The PresidentialGreen Chemistry ChallengeAwards ProgramSummary of 1996 AwardEntries and Recipients

United StatesEnvironmental ProtectionAgency

EPA744-K-96-001July 1996

Office of PollutionPrevention and Toxics(7406)

1EPA

2 Printed on paper that contains at least 20 percent postconsumer fiber.

The Presidential Green ChemistryChallenge Awards ProgramContents

Awards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2

Alternative Synthetic Pathways Award . . . . . . . . . . . . . . . . . . . . . . . . .2

Alternative Solvents/Reaction Conditions Award . . . . . . . . . . . . . . . .3

Designing Safer Chemicals Award . . . . . . . . . . . . . . . . . . . . . . . . . . . .4

Small Business Award . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5

Academic Award . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7

Entries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8

Entries from Academia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8

Entries from Small Businesses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12

Entries from Industry and Government . . . . . . . . . . . . . . . . . . . . . . .16

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .45

The Presidential Green ChemistryChallenge Awards ProgramSummary of 1996 Award Entries and Recipients

President Clinton announced the Green Chemistry Challenge on March16, 1995, as one of his Reinventing Environmental Regulations Initiatives.According to President Clinton, the Green Chemistry Challenge was estab-lished to “promote pollution prevention and industrial ecology through anew U.S. Environmental Protection Agency (EPA) Design for theEnvironment partnership with the chemical industry.” More specifically, theprogram was established to recognize and support fundamental and innova-tive chemical methodologies that are useful to industry and that accomplishpollution prevention through source reduction.

EPA Administrator Carol Browner announced the Green ChemistryChallenge Awards Program on October 30, 1995. She described the programas an opportunity for individuals, groups, and organizations “to compete forPresidential awards in recognition of fundamental breakthroughs in cleaner,cheaper, smarter chemistry.” The Green Chemistry Challenge AwardsProgram provides national recognition for technologies that incorporategreen chemistry principles into chemical design, manufacture, and use.

Entries received for the 1996 Presidential Green Chemistry ChallengeAwards were judged by an independent panel of technical experts convened bythe American Chemical Society. The criteria for judging included health andenvironmental benefits, scientific innovation, and industrial applicability. Fiveprojects that best met the scope of the program and the criteria for judging wereselected for the 1996 Awards and nationally recognized on July 11, 1996.

This document provides a collection of summaries of the entries received forthe 1996 Presidential Green Chemistry Challenge Awards. The approachesdescribed in these summaries illustrate how numerous individuals, groups, andorganizations from academia, small businesses, industry, and government aredemonstrating a commitment to designing, developing, and implementinggreen chemical methodologies that are less hazardous to human health and theenvironment. The approaches described in these summaries also illustrate thetechnical and economic feasibility of implementing green chemical methodolo-gies and are recognized for their beneficial scientific, economic, and environ-mental impacts.

Note: The summaries provided in this document were obtained from the entries received for the 1996Presidential Green Chemistry Challenge Awards. They were edited for space, stylistic consistency, andclarity, but they were not written by nor are officially endorsed by EPA. In many cases, these summariesrepresent only a fraction of the information that was provided in the entries received and as such, areintended to highlight the nominated projects, not describe them fully. These summaries were not used inthe judging process; judging was conducted on all information contained in the entries received. Claimsmade in these summaries have not been verified by EPA.

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2

Alternative Synthetic Pathways Award

The Catalytic Dehydrogenation of Diethanolamine

Disodium iminodiacetate (DSIDA) is a key intermediate in the produc-tion of Monsanto’s Roundup® herbicide, an environmentally friendly, non-selective herbicide. Traditionally, Monsanto and others have manufacturedDSIDA using a well-known process (Strecker process) requiring ammonia,formaldehyde, hydrogen cyanide, and hydrochloric acid. Hydrogen cyanideis of particular concern because of its extreme acute toxicity, and its userequires special handling to minimize risk to workers, the community, andthe environment. Furthermore, the chemistry involves the exothermic gen-eration of potentially unstable intermediates, and special care must be takento preclude the possibility of a runaway reaction. The overall process alsogenerates up to one kilogram of waste for every seven kilograms of product.Much of this waste contains traces of cyanide and formaldehyde and must betreated prior to safe disposal.

In pursuit of safer and environmentally benign chemistry, Monsanto hasdeveloped and implemented an alternative DSIDA process that relies on thecopper-catalyzed dehydrogenation of diethanolamine (DEA). The raw mate-rials have low volatility and are less toxic than those of other processes.Process operation is inherently safer because the dehydrogenation reactionis endothermic and therefore does not present danger of runaway. Moreover,this “zero-waste” route to DSIDA produces a product stream that, after fil-tration of catalyst, is of such high quality that no purification or waste cut isnecessary for subsequent use in the manufacture of Roundup®. The newtechnology represents a major breakthrough in the production of DSIDAbecause it avoids the use of cyanide and formaldehyde, is safer to operate,produces higher overall yield, and has fewer process steps.

The metal catalyzed conversion of aminoalcohols to amino acid salts wasknown since 1945. However, commercial application of this chemistry wasnot known until Monsanto developed a series of proprietary catalysts thatmake the chemistry commercially feasible. The original dehydrogenativeapproach to amino acid salts had apparently been impracticable because thecatalysts, cadmium, nickel, and copper, are either too toxic, poorly selective,poorly active, and/or physically unstable to be commercially viable. Thepatented improvements on metallic copper catalysts made at Monsantoafford an active, easily recoverable, highly selective, and physically durablecatalyst that has proven itself in large-scale use.

This catalysis technology also can be used in the production of otheramino acids such as glycine. Moreover, it is a general method for conversionof primary alcohols to carboxylic acid salts and is potentially applicable tothe preparation of many other agricultural, commodity, specialty, and phar-maceutical chemicals.

Monsanto Company

3

The Dow ChemicalCompany

Alternative Solvents/ReactionConditions Award

The Development and Commercial Implementation of 100 PercentCarbon Dioxide as an Environmentally Friendly Blowing Agentfor the Polystyrene Foam Sheet Packaging Market

In recent years the chlorofluorocarbon blowing agents used to manufac-ture polystyrene foam sheet have been associated with environmental con-cerns such as ozone depletion, global warming, and ground level smog. Dueto these environmental concerns, the Dow Chemical Company has devel-oped a novel process for the use of 100 percent carbon dioxide CO2.Polystyrene foam sheet is a useful packaging material offering high stiffnessto weight ratio, good thermal insulation value, moisture resistance, and recy-clability. This combination of desirable properties has resulted in the growthof the polystyrene foam sheet market in the United States to over 700 mil-lion pounds in 1995. Current applications include thermoformed meat, poul-try and produce trays, fast food containers, egg cartons, and serviceware.

The use of 100 percent CO2 offers optimal environmental performancebecause CO2 does not deplete the ozone layer, does not contribute to groundlevel smog, and will not contribute to global warming since CO2 will be usedfrom existing by-product commercial and natural sources. The use of CO2

by-product from existing commercial and natural sources such as ammoniaplants and natural gas wells, will ensure that no net increase in global CO2

results from the use of this technology. Carbon dioxide is also non-flamma-ble providing increased worker safety and is cost effective and readily avail-able in food grade quality. Carbon dioxide also is used in such commonapplications as soft drink carbonation and food chilling and freezing.

The use of Dow 100 percent CO2 technology eliminates the use of 3.5 mil-lion pounds per year of hard CFC-12 and/or soft HCFC-22. This technologyhas been scaled from pilot line to full scale commercial facilities. Dow has madethe technology available through a commercial license covering both patentedand know how technology. The U.S. Patent Office granted Dow two patents forthis technology (5,250,577 and 5,266,605).

Designing Safer Chemicals Award

Designing an Environmentally Safe Marine Antifoulant

Fouling, the unwanted growth of plants and animals on a ship’s surface,costs the shipping industry approximately $3 billion a year. A significant por-tion of this cost is the increased fuel consumption needed to overcomehydrodynamic drag. Increased fuel consumption also contributes to pollu-tion, global warming, and acid rain.

The main compounds used worldwide to control fouling are the organ-otin antifoulants, such as tributyltin oxide (TBTO). They are effective at pre-venting fouling, but have widespread environmental problems due to theirpersistence in the environment and the toxic effects they cause, includingacute toxicity, bioaccumulation, decreased reproductive viability, andincreased shell thickness in shellfish. These harmful effects led to an EPAspecial review of organotin antifoulants and to the Organotin AntifoulantPaint Control Act of 1988. This act mandated restrictions on the use of tin inthe United States and charged the EPA and the U.S. Navy with conductingresearch on alternatives to organotins.

Based on the need for new antifoulants, Rohm and Haas Company beganto search for an environmentally safe alternative to organotin compounds.The ideal antifoulant would prevent fouling from a wide variety of marineorganisms without causing harm to non-target organisms. Compounds fromthe 3-isothiazolone class were chosen as likely candidates and over 140 werescreened for antifouling activity in laboratory and field tests. The 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Sea-NineTM anti-foulant) was chosen as the can-didate for commercial development.

Extensive environmental testing was done comparing Sea-NineTM

antifoulant to TBTO, the current industry standard. Sea-NineTM antifoulantdegraded extremely rapidly with a half life of one day in seawater and onehour in sediment. TBTO, on the other hand, degraded much more slowly,with a half life in seawater of nine days and six to nine months in sediment.Tin bioaccumulated, with bioaccumulation factors as high as 10,000 X, whileSea-NineTM antifoulant’s bioaccumulation was essentially zero. Both TBTOand Sea-NineTM were acutely toxic to marine organisms, but TBTO hadwidespread chronic toxicity, while Sea-NineTM antifoulant showed no chron-ic toxicity. Thus the maximum allowable environmental concentration(MAEC) for Sea-NineTM antifoulant was 0.63 parts per billion (ppb) while theMAEC for TBTO was 0.002 ppb. Sea-NineTM antifoulant has been soldworld-wide and hundreds of ships have been painted with coatings contain-ing it. Rohm and Haas Company obtained EPA registration for the use ofSea-NineTM antifoulant, the first new antifoulant registration in over a decade.

Rohm and HaasCompany

4

Small Business Award

Production and Use of Thermal Polyaspartic Acid

Millions of pounds of anionic polymers are used each year in many indus-trial applications. Polyacrylic acid (PAC) is one important class of such poly-mers. In many uses, the polymers ultimately end up in a waste treatmentfacility. The ideal disposal for these polymers is via biodegradation bymicroorganisms because the degraded endproducts are innocuous. The dis-posal of PAC is problematic, however, because it is not biodegradable. Aneconomically viable, effective, and biodegradable alternative is thermalpolyaspartate (TPA).

Donlar invented two highly efficient processes to manufacture TPA;patents have either been granted or allowed. The first process involves a dryand solid polymerization converting aspartic acid to polysuccinimide. Noorganic solvents are involved during the conversion and the byproduct iscondensated water. The process is extremely efficient — a yield of more than97 percent of polysuccinimide is routinely achieved. The second step of thisprocess, the base hydrolysis of polysuccinimide to polyaspartate, is alsoextremely efficient and waste free.

The second TPA production process involves using a catalyst during thepolymerization, which allows a lower heating temperature to be used. Theresulting product has improvements in performance characteristics, lowercolor, and biodegradability. The catalyst can be recovered from the process,thus minimizing waste.

Independent toxicity studies of commercially produced TPA have beenconducted using mammalian and environmental models. Results indicatethat TPA is non-toxic and environmentally safe. TPA biodegradability alsohas been tested using established OECD methodology, performed in anindependent laboratory. Results indicate that TPA meets OECD guidelinesfor Intrinsic Biodegradability. PAC can not be classified as biodegradablewhen tested under the same conditions.

Many end uses of TPA have been discovered. In the agricultural sector,the use of high levels of fertilizer has been practiced to sustain crop yields.However, the efficiency of fertilizer usage is generally low and unused fertil-izer can cause not only economic loss, but has an undesirable impact on theenvironment. Therefore, a better fertilizer management strategy is warrant-ed to sustain crop yields and lessen the negative environmental impact of fer-tilizer runoff. TPA can be an ideal candidate to improve fertilizer or nutrientmanagement because it increases the efficiency of plant nutrient uptake,which not only assists in sustaining the nutrient sources, but also protects theecology of the agricultural land, while at the same time bringing economicbenefits in the form of increased crop yields.

Donlar Corporation

5

6

TPA also can be used in the water treatment industry. TPA can be usedas mineral scale inhibitors for calcium carbonate, calcium sulfate and bariumsulfate. The efficacy of TPA has been tested extensively and compared withPAC, the industry standard. Results indicate that TPA is as good as, and inmany instances outperformed, PAC.

There are additional uses for TPA. In the detergent industry, TPA can beused as an anti-redeposition agent; its efficacy is again comparable to PAC.In the oil and gas production industry, TPA can serve as scale and corrosioninhibitors, reducing the need for toxic corrosion inhibitors and lessen theneed for waste treatment.

TPA is an ideal candidate for use in water treatment, agriculture, andother industries. The processes to manufacture TPA are economically viableand TPA is proven to be biodegradable, non-toxic, and effective.

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Academic Award

Conversion of Waste Biomass to Animal Feed, Chemicals, and Fuels

A family of technologies has been developed at Texas A&M that convertswaste biomass into animal feed, industrial chemicals and fuels. Waste bio-mass includes such resources as municipal solid waste, sewage sludge,manure, and agricultural residues. Currently these resources are under-uti-lized; in fact, many have a cost associated with their disposal. Waste biomassis treated with lime to render it more digestible. Lime-treated agriculturalresidues (e.g. straw, stover, bagasse) may be used as ruminant animal feeds.Alternatively, the lime-treated biomass can be fed to a large anaerobic fer-mentor in which rumen microorganisms convert the biomass into volatilefatty acid (VFA) salts such as calcium acetate, propionate, and butyrate. TheVFA salts are concentrated and may be converted into chemicals or fuels viathree routes. In one route, the VFA salts are acidified releasing acetic, pro-pionic, and butyric acids. In a second route, the VFA salts are thermally con-verted to ketones such as acetone, methyl ethyl ketone, and diethyl ketone.In a third route, the ketones may be hydrogenated to their correspondingalcohols such as isopropanol, isobutanol, and isopentanol.

This family of technologies offers many benefits for human health and theenvironment. Lime-treated animal feed can replace feed corn, which isapproximately 88 percent of corn production. Growing corn requires plow-ing, which exacerbates soil erosion; approximately two bushels of top soilare lost for each bushel of corn harvested. Also, corn requires intensiveinputs of fertilizers, herbicides, and pesticides, all of which are contaminat-ing ground water.

Chemicals (e.g. organic acids and ketones) may be produced economi-cally from waste biomass that has a negative impact on the environment,such as municipal solid waste and sewage sludge. Typically, these wastes arelandfilled or incinerated, which incurs a disposal cost while contributing toland or air pollution. By producing chemicals from biomass, nonrenewableresources such as petroleum and natural gas, are conserved for later genera-tions. Because 50 percent of U.S. petroleum consumption is now imported,displacing foreign oil will help reduce the U.S. trade deficit.

Fuels (e.g. alcohols) produced from waste biomass have the benefits citedabove, i.e., reduced environmental impact from waste disposal and reducedtrade deficit. In addition, oxygenated fuels derived from biomass are clean-er burning and do not add net carbon dioxide to the environment, therebyreducing factors that contribute to global warming.

Professor

Mark Holtzapple,

Department of Chemical

Engineering,

Texas A&M University

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Entries from Academia

Derivatized and Polymeric Solvents for Minimizing Pollution During the Synthesis of Pharmaceuticals

A new class of solvents has been developed that have solvation propertiessimilar to those of solvents used conventionally in chemical synthesis, sepa-rations and cleaning operations, but for which the potential for loss by envi-ronmentally-unfavorable air emissions or aqueous discharge streams isminimized. These solvents are derivatives of solvents currently used in reac-tion and separation processes, tailored such that they are relatively non-volatile and non-water soluble, thereby satisfying the criteria for pollutionsource reduction. The solvents can be used as neat reaction or separationmedia, or they can be diluted in an inert environment such as higher alka-nes. Polymeric or oligomeric solvents such as derivatized THF have beensynthesized using macromonomers incorporating the desired functionality.These polymeric solvents are easily recovered using mechanical separationssuch as ultrafiltration rather than energy-intensive distillation processes. Thisnew concept for solvent design and synthesis offers the potential for significantsource reductions in air and water pollution and can be considered to be wide-ly applicable to fine chemical and pharmaceutical synthesis, separations, andcleaning operations.

Environmental Advantages Offered by Indium-PromotedCarbon-Carbon Bond-Forming Reactions in Water

The development of effective carbon-carbon bond forming reactions inaqueous media is imperative for the future welfare and growth of the chem-ical industry. The metal indium, a relatively unexplored element, has recent-ly been shown to offer intriguing advantages for promoting organictransformations in aqueous solution. The feasibility of performingorganometallic/carbonyl condensations in water, for example, has beenamply demonstrated for the metal indium. Indium is non-toxic, very resis-tant to air oxidation, and easily recovered by simple electrochemical means,thus permitting its re-use and guaranteeing uncontaminated waste flow. Inaddition, protection-deprotection of functional groups and an inert atmos-phere are not necessary when implementing this technology. Commercialapplication is immediately possible for this exciting new chemistry and mayhave been implemented already. As additional progress is made, adaption toexisting procedures will undoubtedly come quickly.

Enzyme-Assisted Conversion of Aromatic Substances toValue-Added End Products. Exploration of Potential Routes toBiodegradable Materials and New Pharmaceuticals

The combination of enzymatic transformations performed in aqueousmedia with efficacious, brevity-based design has been shown to yieldunprecedented efficiency in the attainment of important pharmaceuticals

Professor

Tomas Hudlicky,

Department of Chemistry,

University of Florida

Professor

Leo A. Paquette,

Department of Chemistry,

Ohio State University

Professor

T. Alan Hatton,

Department of Chemical

Engineering,

Massachusetts Institute of

Technology

Professor

Stephen L. Buchwald,

Chemistry Department,

Massachusetts Institute of

Technology

from metabolites of the arene cis-diol type, more than 200 of which areknown. Such processes lead to pollution reduction at the manufacturingsource by drastically shortening the synthetic process, thus requiring lessreagent and solvent input. Because one or more steps are performed in waterwith whole cells of common soil bacteria, the residual mass of such steps is,after sterilization, judged suitable for disposal to municipal sewers, thus fur-ther reducing the amount of actual waste. This program has potentially glob-al impact with attendant benefits to the health and economy of society atlarge through managed processing of aromatic waste.

Green Technology for the 21st Century: Ceramic Membranes

Advancing technology in the areas of remediation and such “green” engi-neering tools as ceramic membranes can make a significant contribution interms of environmental clean-up and a healthier world. Ceramic membranesrepresent a relatively new class of materials that can be produced from avariety of starting materials and processed in different ways to yield productswith a broad range of physical-chemical characteristics and an equally largerange of applications. The robust character of ceramic membranes enablesthem to withstand broad pH and temperature ranges, elevated pressures,organic solvents, and chemical and heat sterilization. In addition, pore sizecan be controlled in these materials and is typically 5-100 Å in diameter.These characteristics indicate that ceramic membranes could replace theirorganic polymeric counterparts in many applications where conditionswould otherwise preclude using an organic polymer membrane. These appli-cations include separations, catalysis, photocatalysis and energy storage sys-tems for solar cells and micromotor devices. Ceramic membranes are acutting edge technology that could well provide economic growth for exist-ing industries, in addition to facilitating new growth industries in environ-mental remediation. A market survey published in 1992 on the economicbenefits from alternate applications of inorganic membrane technology indi-cated that active implementation of such technology could well result in a $2billion per year sales market, a $16.6 billion increase in the national GDP, a$2 billion improvement in the balance of trade, and a decrease in energy useof 6 quads per year.

A Nontoxic Liquid Metal Composition for Use as a Mercury Substitute

Mercury is used extensively in switches and sensors, but is toxic to humansand animals. In addition to being an excellent conductor of electricity, mer-cury has significant surface tension and, unlike any other metal known,remains fluid throughout a wide temperature range which encompasses 0°C.Because of these properties, mercury is found in numerous commercial prod-ucts such as automobiles, thermostats, steam irons, pumps, computers, andeven in tennis shoes. In each of these cases mercury functions as a liquid elec-trical switch. Since billions of mercury switches are made worldwide each year,a non-toxic replacement appears highly desirable. A nontoxic, cost effectivealternative to mercury that has comparable performance characteristics hasbeen identified at Virginia Tech. This green technology provides a gallium

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Professor

Marc A. Anderson,

Water Chemistry Program,

University of Wisconsin-

Madison

Professor

Larry T. Taylor,

Department of Chemistry,

Virginia Tech

Virginia Tech Intellectual

Properties

alloy containing indium, zinc, and copper that conducts electricity, freezesbelow 0°C, exhibits high surface tension, and possesses a very high boilingpoint and very low vapor pressure. In addition, non-mercury switches and sen-sors can replace mercury switches and sensors without modifying existing tech-nology. Mercury also is used in temperature sensors, pressure activatedswitches, pumps and filters, slip rings, liquid mirror telescopes, fluid unions,dental amalgam, and in medical devices such as sphygmomanometers andbougies. The non-mercury material also can serve as a substitute for elementalmercury in a many of these applications.

Rational Design of Catalytic Reactions for Pollution Prevention

Chemical products manufacturing is a major industrial source of toxic andhazardous chemicals. Catalytic technologies hold the key to the developmentof more environmentally benign chemical processes and for the continuedimprovement of existing processes. Historically, the design of chemical syn-thesis catalysts was extraordinarily empirical. Yield of desired products andoperational characteristics were normally optimized based on suites of experi-ments run on catalysts made from various manufacturing conditions andblends. The ability to correlate catalyst behavior to catalyst surface featureswas extremely limited. Accordingly, predicting the desired catalyst features fora given application and from that, formulating a catalyst manufacturing strate-gy, was essentially beyond reach. Moreover, the concept of redesigning cata-lysts so as to inhibit the formation of undesired coproducts, toxic materials, andwasteful pollutants was fanciful. A methodology for Rational CatalystTechnologies has been developed at the University of Wisconsin that makes itpossible to design and optimize catalysts by first understanding the nature ofthe desired catalyst surface and from that formulate the catalyst. This strategyfor the rational design of catalytic reactions has found wide acceptance world-wide and has been applied successfully to link surface science research to thedevelopment of industrially important catalytic chemical reactions. Industrialcollaborations and/or applications include ammonia catalysis, the environ-mental de-NOx reaction, the water gas shift reaction on magnetite, titania sur-face species, molybdena and vanadia catalysts for clean partial oxidation ofmethane, and hydrocarbon cracking over acid Y-zeolite catalysts for the cleanproduction of isobutylene.

The Replacement of Hazardous Organic Solvents with Water in theManufacture of Chemicals and Pharmaceuticals

The use of water as the primary solvent is a realistic approach to greenchemistry and is a very desirable approach for reducing hazardous organic sol-vents from plant inventories. Multiphase reactors have been developed at theNew Jersey Institute of Technology and other universities that use water as thereaction medium in order to avoid the use of hazardous organic solvents in themanufacture of pharmaceuticals and specialty chemicals. The technology is thefirst to show that free radical bromination of organics can be carried out inaqueous systems. A unique semi-continuous droplet reactor also has beendeveloped for epoxidations. Before pollution prevention became fashionable,organic chemists found that water-based reactions gave higher yields at faster

Professor

Henry Shaw,

Chemistry and

Environmental Science

Department,

New Jersey Institute of

Technology

Dr. Dan Watts,

Center for Environmental

Engineering and Science,

New Jersey Institute of

Technology

10

Professor

James A. Dumesic,

Chemical Engineering

Department,

University of Wisconsin

Dr. John C. Crittenden,

National Center for Clean

Industrial and Treatment

Technologies,

Michigan Technological

University

rates under milder conditions than organic solvent-based reactions. This isincentive enough for process change. The fact that these methods offer a new“non-end-of-pipe” method of eliminating VOC’s adds a major incentive forprocess modification.

Soapy CO2

Carbon dioxide surfactant technology, or “soapy CO2”, has demonstratedthe utility of replacing less acceptable organic chemicals with liquid/supercrit-ical CO2 and thus can have a very positive environmental impact. Carbondioxide represents an environmentally friendly alternative to the solvents cur-rently used in a variety of applications. In order to expand the use of liquid andsupercritical CO2, its solvating power for large, hydrocarbon based moleculesmust be enhanced. The key to this technology is the development of surfactantsystems for CO2 as well as establishing the underlying principles involved withCO2-surfactant combinations. In addition to polymerization processes, tech-nology extensions of this project are relevant for CO2 as a cleaning and extrac-tion media (replacing halogenated hydrocarbons) as well as a solvent/mediafor organic reactions. In all of these applications, the production and emissionof hazardous waste would be significantly reduced by replacing the currenttechnology with carbon dioxide surfactant technology. It must be noted thatCO2 is readily available as a waste gas from various sources. Thus no new CO2

will be produced due to the success of the technology — it will just be borrowedfrom the environment for an interim period of time.

The SYNGEN Program for Generation of Alternative Syntheses

The SYNGEN program attempts to survey all possible synthetic routes toa target molecule and reduce the vast number of these possibilities quicklyand stringently to focus on only the shortest and cheapest routes. The pro-gram first focuses on minimizing steps and the central role of prior skeletaldissection to find the best assemblies of the target skeleton from availablestarting skeletons. It then presents the ideal synthesis, of construction reac-tions only, to create the target just by sequential constructions uniting thesestarting skeletons. Finally, the digital basis rigorously, but concisely, definesall possible molecular structures and their reactions. This basis allows thenew SYNGEN program to propose all the short alternative syntheses of anyproduct from real starting materials in terms of both their cost and environ-mental impact.

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Professor

Joseph DeSimone,

Department of Chemistry,

University of

North Carolina at

Chapel Hill

Air Products and

Chemicals, Inc.

Professor

James B. Hendrickson,

Department of Chemistry,

Brandeis University

Entries from Small Businesses

Catalytic Extraction Processing

Catalytic Extraction Processing (CEP) is a proprietary technology thatuses secondary materials and by-products (that might otherwise be consid-ered ‘wastes’) as raw materials in a manufacturing process. CEP manufac-tures commercial products (i.e., industrial gases, alloys, and ceramics) fromheterogeneous organic, organometallic, and inorganic materials using amolten metal bath as both catalyst for elemental dissociation and a solutionfor reaction engineering. CEP feed materials go through two stages in themetal bath: dissociation and dissolution of molecular entities to their ele-ments and reaction of these elemental intermediates to form products. Thewaste minimization and environmental performance of CEP is ensured bythe separation of feed from product through elemental dissociation and thepredictable partitioning afforded by the control of thermodynamic operatingconditions. Employed as an off-site, closed-loop process unit, CEP maxi-mizes environmental performance for a broad spectrum of secondary mate-rials and by-products through pollution prevention, waste minimization, anddecreased demand on ever-diminishing natural resources.

Cross-Linked Enzyme Crystal Technology

Enzymes are proteins that can function as highly efficient and selectivecatalysts. They have evolved over billions of years to facilitate the myriad ofbiochemical reactions essential to life, and as such, they are compatible bydefinition with living organisms. The benefits of enzyme technology havelong been recognized, but to date, the chemical and physical stability ofenzymes has not approached that of conventional heterogeneous catalysis.Crosslinked Enzyme Crystals (CLEC) are novel catalysts that are suitable forchemical manufacturing, diagnostic instruments, therapeutics, and for thedetoxification of hazardous materials. The concept of CLEC emerged fromthe realization that protein crystals grown for structural studies using X-raydiffraction were also macroscopic particles that, if properly stabilized, mightpresent a new and robust class of immobilized enzymes. By extension of thissimple idea, CLECs have been developed that circumvent many of the prac-tical problems associated with enzyme use. In addition to being environ-mentally benign, enhanced properties of CLECs include superior catalyticperformance, operating stability, storage stability, compactness, superior uni-formity, and operational convenience.

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Molten Metal

Technology, Inc.

Altus Biologics Inc.

Development of a Biodiversity Search and Enzyme Optimization Technology

Biocatalysis is widely regarded as a promising new approach to sourcereduction of pollution associated with chemical manufacturing. It has notbeen widely adopted to date, however, due to the limited availability ofprocess-compatible biological catalysis. Recombinant Biocatalysis, Inc.(RBI), has developed a whole new tool kit of biological catalysis for chemists.Catalysts are central to modern chemical manufacturing as well as to life. Agood catalyst accelerates the rate of a desired reaction compared to unwant-ed, waste generating, side reactions. Enzymes are wonderfully selective andspecific catalysts. Enzymes, however, evolved to work in living systems, andenzymes that work well in a chemical process plant have not been broadlyavailable to chemists and chemical engineers. RBI has developed a newtechnology specifically to meet that unmet need. By turning state-of-the-artbiotechnology to the problem of making useful enzymes for chemists, RBIhas enabled a step change in the availability of useful protein-based catalystsfor the chemical process industry. RBI has developed and applied a power-ful, new biodiversity search technology to scan natural sources for newenzymes. Once the best enzyme that nature has to offer for a particular appli-cation is identified, RBI applies additional high throughput technology tooptimize the enzyme to make it more useful in a chemical plant. This newtechnology already has produced more than 150 new, robust biological cat-alysts for the chemical process industry and will generate more than 3,000 by1997.

Development of a Nickel Brightener Solution

Historically, electroplaters of duplex nickel had to use formaldehyde andcoumarin-bearing nickel plating solutions to obtain a non-sulfur nickel deposit,which is essential to the duplex nickel process, for maximum corrosion pro-tection of external automotive trim and bumpers. The Watts’ bath, introducedin 1916, made it possible to increase the speed of nickel deposit by a factor often by increasing the electrical current density. This development lead to themodern bright nickel plating baths known today, using organic and inorganicadditives. Organic aromatic sulfonic acid was later introduced to the Watts’bath to achieve the first practical bright nickel plating solution. In 1936,formaldehyde was added to the solution followed in rapid succession by otheradditives. Coumarin, along with formaldehyde, became the important ingre-dients in a variety of nickel plating baths referred to as “semi-bright”. Today,semi-bright nickel plating occupies an important position in plating.Benchmark Products has developed a nickel brightener solution that, whileimproving the performance of electroplating, also significantly reduces theenvironmental impact by eliminating two toxic ingredients, formaldehyde andcoumarin, and substituting non-hazardous ingredients.

13

RecombinantBioCatalysis,

Inc. (RBI)

Benchmark Products, Inc.

14

Enviroblock Technology

Using a new pulverization technology, all types of scrap glass can be groundinto a useful aggregate with the consistency of beach sand or fine gravel. Anysize or form of flat window glass, mirrors, windshields, light bulbs, bottles,neon tubing, or glass containers can be processed back into a usable form.Scrap glass is fed to an EVIROGRINDER pulverizing machine which deliv-ers a controlled particle size material. A fine grind sand product is then fed toa blending machine, the ENVIROMIXER, which dry blends the two basicsubstances, ground glass and a reactive binder. These mixed materials areplaced inside the ENVIROPACTOR machine to form blocks. Hard, dense,naturally insulative/smooth faced blocks are rapidly compacted at low costand high volume with a yield of 400 to 600 blocks per hour. Walls built withglass blocks reduce heating and air conditioning because glass is a natural insu-lation source. Glass blocks are waterproof, fireproof, strong, and reduce ener-gy consumption.

National Conversion to Low Sudsing Hand Dish Detergents forIndustrial, Institutional, and Especially Consumer Application

In the United States, almost all dish detergents or liquid detergents used forhand dish washing are anionic based, with specifically high foaming propertiesformulated purposely into the product to deliver a consumer aesthetic. To pro-vide this sudsing characteristic, multiple anionic and foam boosters areused/needed to deliver the effect. The addition of all these extra chemicals isunnecessary to deliver actual cleaning performance and oily soil emulsifica-tion. This can be achieved by using nonionic surfactants, straight chain linearalcohol ethoxylates or APGs (alkyl polyglycosides) or other low foaming envi-ronmentally suitable alternatives to alkylbenzene sulfonate and foam boostersformulation types. Nationwide use of this technology in all dish detergentswould reduce overall toxicity due to the discharge of high sudsing dish prod-ucts in rivers and streams. In addition, overall water usage would decrease dueto faster manufacturing and overall reduced energy consumption of operationsproviding this product category to all U.S. market sectors: consumer, industri-al, and institutional. This formulation strategy can be available immediatelynationwide and can be manufactured readily by all national brand companies.

Stanson Corporation

Zeller International

15

A Non-Toxic, Non-Flammable, Aqueous-Based Cleaner/Degreaserand Associated Parts Washing System Commonly Employed inAutomotive Repair Industry

An aqueous based cleaner and associated parts washing system common-ly employed in the automotive repair industry has been developed that elim-inates the generation of hazardous waste associated with current parts washsystems. Currently, the majority of parts washers employ a “StoddardSolvent” which, when spent, is manifested as a hazardous waste to a distilla-tion facility which separates the solvent from the petroleum residue. The newtechnology employs a non-toxic, non-flammable, aqueous basedcleaner/degreaser that can be recycled continuously on site by employingoil/water separation and standard combustion engine filters. Both the oil sep-aration and filtration apparati are housed within a recently developed partswasher unit, such that the aqueous cleaner/degreaser is recycled in-situ, elim-inating the removal and/or transportation and special treatment of spentcleaner material off-site. Testing results have shown that (i) the resulting oilskimmed from the cleaner can, under current hazardous waste definitions, bemanaged as a “spent oil” and combined with spent engine oil for beneficialreuse as a secondary fuel, and (ii) the filter can be managed under currentmethods used to recycle other used combustion engine oil filters. CircuitResearch Corporation believes there are in excess of 7,000 parts washers inMinnesota generating approximately 1.5 million gallons of spent Stoddardsolvent annually. Circuit Research Corporation’s alternative technology couldsignificantly reduce the generation of this waste.

Circuit ResearchCorporation

16

Entries from Industry and Government

Aldimine-Isocyanate Chemistry: a Foundation forEnvironmentally-Friendly High Solids Coatings

The single greatest challenge that the chemical industry faces today is thedesign and manufacture of new chemicals that are not only efficacious, butjust as importantly, environmentally friendly. Within the coatings industry,these new chemicals play the additional role of aiding in pollution preven-tion by reducing the amount of volatile organic compounds (VOCs) in theform of solvents, materials that traditionally have been used at high levels.The need for raw materials that reduce solvent demand and yet maintain orpreferably improve coating performance is of primary importance.Commercial coatings systems based on aldimine-isocyanate chemistry havebeen developed and are finding widespread acceptance as a solution to VOCrestrictions. Current applications exist in the automotive refinish businesswhere aldimines are used to make coatings containing only 20 to 25 percentvolatile solvents, replacing products that have 40 to 50 percent volatile sol-vents by weight. Since the introduction of this technology in 1995, old tech-nology resin systems requiring more than 100,000 kilograms of additionalorganic solvent have been displaced. This volume will triple in 1996 andapproach one million kilograms in 1997. More importantly, the volume oforganic solvents displaced as other market areas adopt this technology isexpected to increase dramatically. Additional benefits of this technologyinclude: allowing low VOC coatings to be developed, resulting in large sol-vent savings for a given application without transferring environmental lia-bility to production or use; it is already in significant commercial use, andwill become a high volume product line by the end of the century, resultingin nontrivial source reduction of organic solvent emissions; it is compatiblewith existing and future coatings systems; it does not require significant cap-ital investment to employ; and it increases productivity.

Alkyl Polyglycoside Surfactants

Henkel Corporation’s alkyl polyglycoside (APG®) surfactants are a classof non-ionic surfactants marketed to the detergent and personal care indus-tries. APG® surfactants are manufactured from renewable resources: fattyalcohol, derived from coconut and palm oils, and glucose, derived from cornstarch that is supplied from U.S. sources. APG® surfactants have very lowecotoxicity and are readily biodegradable and, therefore, are more innocu-ous to the environment than alternative petrochemical-based technologies.In addition to the environmental friendliness of the chemistry, APG® surfac-tants demonstrate the following benefits in detergent and personal care appli-cations: reduction of overall chemical consumption by improving thecleaning efficiency in detergent formulations; reduction of formulated prod-uct packaging waste by permitting the formulation of concentrated cleaningproducts; reduction of formula stabilizing adjuncts (hydrotropes), such assodium xylene sulfonate and ethanol, that do not contribute to cleaning per-

Henkel Corporation, Emery Group

Bayer Corporation

17

formance and, in the case of ethanol, increase volatile organic emissions; andexcellent cleaning performance with lower skin and eye irritation comparedto other surfactants. APG® surfactants represent an important application ofgreen chemistry that uses renewable resources. APG® surfactants are cur-rently manufactured in a new plant producing 50 million pounds per yearfor use in the formulation of several hundred detergent and personal careproducts in the United States and worldwide.

The Alternative Feedstocks and Biological and ChemicalTechnologies Research Programs

The Alternative Feedstocks (AF) program supports development workthat employs alternative, renewable feedstocks in the biological and/orchemical production of commodity or commodity-like chemicals. TheBiological and Chemical Technologies Research (BCTR) program supportsresearch and development efforts that provide evidence of the technical andeconomic feasibility of advanced chemical and biological concepts thatimprove energy utilization, operational efficiencies, and environmentalsoundness of current U.S. industry process operations. These two programsinvolve both the specific and broad utilization of “green chemistry” in thefulfillment of their missions. By definition, the AF program is green chem-istry since it promotes the use of renewables in producing subsidy-free chem-icals from feedstocks such as corn, lignocellulosics, and oil seed crops onscales that are or could be commodity chemicals. Many of the technologyhurdles needed to employ biocatalysts as tools or biomass as a feedstockresource for the chemical processing industry have been addressed by theBCTR program. For example, efforts ranging from the development of mol-ecular modeling tools to new, less toxic electrochemical hydrogenationprocesses have been undertaken and demonstrated for use in currentprocesses. Within the federal sector, these two programs have an exception-al history of applying green chemistry to industrial needs.

An Alternative Solvent, Isomet

The Bureau of Engraving and Printing, the world’s largest securities man-ufacturing establishment, produces currency, postage stamps, revenuestamps, United States Saving Bonds, and other government securities. Until1990, the Bureau used Typewash for cleaning the typographic seals, serialnumber, numbering blocks of the Cop-Pack (overprinting presses) andpostage stamp printing presses. Typewash is a solvent mixture of methylenechloride (55 percent), toluene (25 percent) and acetone (20 percent). As ofSeptember 1, 1990, this solvent is no longer in compliance with District ofColumbia Environmental Law and Federal Air Toxic Law. An alternativesolvent, Isomet was developed by the Bureau of Engraving and Printing toreplace Typewash. Isomet is a mixture of synthetic isoparaffinic hydrocarbon(55 percent), propylene glycol monomethyl ether (10 percent), and isopropylalcohol. Initial testing of Isomet found the solvent to be a highly successfulreplacement for Typewash and less costly than any commercially availablesolvent. Isomet was found to be acceptable in cleaning ability, solvent evap-oration rate, solvent odor, environmental and safety compliances, and cost.

U.S. Department ofEnergy, Office of

IndustrialTechnologies

Programs

Bureau of Engraving and

Printing, Office ofResearch and

Technical Support

18

Isomet is currently used for cleaning all Bureau postage stamp and over-printing presses. Thus a solvent discharged at the rate of 5,000 gallons peryear was made environmentally friendly.

An Alternative Synthesis of Bisnoraldehyde, an Intermediate toProgesterone and Corticosteroids

For the past 40 years, the steroidal intermediate bisnoraldehyde (BNA)has been made and used at Pharmacia and Upjohn to produce bulk phar-maceutical steroids like progesterone and corticosteroids. Recently, anentirely new route to BNA from waste soya bean residues was implementeddue to the development of an environmentally acceptable and efficientchemical process for the oxidation of an intermediate, referred to as bisno-ralcohol (BA), to bisnoraldehyde. The new process uses commercial strengthbleach and a catalyst/co-factor system (4-hydroxy-TEMPO) and is run in atwo-phase reaction medium. This new route to BNA has many humanhealth and environmental benefits because it: avoids using heavy metalbased oxidants such as hexavalent chromium salts and complexes, man-ganese oxides, or lead salts; does not produce noxious emissions unlike oxi-dations which use activated dimethylsulfoxide, dimethylsulfide, orcomplexes of sulfur trioxide; does not use toxic or hazardous materials likeorganic peroxides, organoselenium compounds, or chlorinated quinones;avoids potentially hazardous reaction mixtures like those used for ozonoly-sis, or oxidative dehydrogenation with metal oxides; increases utilization ofsoya sterol feedstock from 15 percent to 100 percent; produces non-toxicaqueous process waste streams and recoverable organic solvent wastestreams; eliminates a process with a running, recycled inventory of 60,000gallons of ethylene dichloride (EDC), a known carcinogen, and that needsup to 5,000 gallons of EDC input annually; produces the same productamount as the previous route with 89 percent less non-recoverable organicsolvent waste and 79 percent less aqueous waste; and has the chemical selec-tivity required for high quality bulk pharmaceutical manufacture. In additionto being a new synthetic route for converting soya sterols to therapeuticsteroids, this chemical process is also a general method for converting pri-mary alcohols to aldehydes that is environmentally superior to currentlyavailable oxidation methods.

Application of Freeze Drying Technology to the Separation ofComplex Nuclear Waste

The nuclear industry must comply with increasingly stringent standardsfor radioactive material levels present in liquid effluents. Current conven-tional methods of decontamination include distillation, ion exchange, pre-cipitation reactions, or chelating agents. Freeze drying technology (FDT) hasbeen applied to the decontamination of radioactive liquids and shown to bethousands of times more effective than conventional methods. Distillation,ion exchange, and chelating agents often require multiple passes, andbecause additional components (resins or chelating agents, which in turn

Los Alamos NationalLaboratory

Pharmacia and Upjohn, Inc.

19

must be disposed as radioactive) are typically needed by these methods,reductions in the volume of radioactive waste are rarely realized. FDT willefficiently separate solvents and volatile acids from complex waste solutionsand process liquids. The separated liquids will be virtually free of radioactivecontamination and can be re-used or discarded as nonradioactive. FDT willdrastically reduce the volume of radioactive wastes. Volume reductionsgreater than one thousand times have been achieved in aqueous solutions, butthe exact volume reduction of nuclear waste will depend on its moisture con-tent. FDT will eliminate the need for storage or destruction of the liquid com-ponent and will lower transportation costs because of volume and weightreductions. In addition, this technology can be considered safe; no high tem-peratures or pressures are used. The process occurs in a vacuum, so the fail-ure of a component would lead to an inward leak and the potential forcontamination outside the system is significantly reduced. Finally, the refrig-erant used in this technology is environmentally friendly liquid nitrogen.

Application of Green Chemistry Principles to Eliminate AirPollution from the Mexican Brickmaking Microindustry

A new recirculating design for small brickmaking kilns has been investi-gated as an alternative to conventional operations, which are a significantsource of air pollution. The bricks used in building many houses and officesbuildings in Mexico and other parts of the third world are typically made byhand and fired in a small kiln using available fuels such as sawdust, treatedwood, paper, trash, tires, plastic, and used motor oil. Although these brickscost about of standard high-fired construction bricks, they do not meet theminimum strength requirements for commercial construction in the UnitedStates. In addition, a major by-product of this brickmaking industry is a highlevel of air pollution—both particulates and toxic chemicals—that results frominefficient thermal design and use of cheap but readily available fuels. Thisindustry is the third leading cause of air pollution in the El Paso-Juárez area.Redesign of the kilns to allow efficient energy recovery and to eliminate wastefrom over- and under-firing makes the use of non-polluting fuels (natural gas)economically attractive. The design challenge is to use inexpensive, readilyavailable materials and equipment to avoid significant capital outlay.Laboratory investigations and process modeling have been performed at theLos Alamos National Laboratory, and field tests are being performed atECOTEC in Ciudad Juárez, Mexico, in cooperation with FEMAP, a privatefoundation in Mexico, and with the El Paso Natural Gas Company. The directbenefits of these improvements in the brickmaking process are reduced airpollution, safer operating conditions, and better bricks. In addition, processmodeling indicates that fuel consumption can be reduced by approximately55 percent and cost analyses project that this will result in an increase in prof-it for the brickmakers of about 35 percent.

Los Alamos NationalLaboratory

20

Asarco Incorporated

Application of Microchemistry Technology to the Analysis ofEnvironmental Samples

“Green” chemistry is an umbrella term addressing such related conceptsas waste minimization, pollution prevention, solvent substitution, environ-mentally conscious manufacturing, maximum atom utilization, technologiesfor a sustainable future, environmental security, and industrial ecology.Another applicable concept, microscale chemistry (or microchemistry), is theapplication of chemical principles and apparatus at a scale much smallerthan currently employed by most bench chemists, thus reducing the volumeof reagents and product by several orders of magnitude. Microscale andgreen chemistries both incorporate waste minimization, pollution preven-tion, and solvent substitution. Adoption of green and microscale methods isincreasingly essential for the environmental analytical community as regula-tions tighten, the costs of waste disposal escalate, and public scrutiny increas-es. By applying green chemistry principles and using advances in separationscience, instrumentation, microscale techniques, and solvent substitution,chemists at Argonne National Laboratory have developed trace environ-mental analysis methods that incorporate source reduction. The techniquesreduce or eliminate the use of hazardous solvents, decrease analysis turn-around time, and significantly reduce the generation of secondary wastesassociated with analytical processing. The success of these methods exem-plifies the opportunities to reduce waste generation at analytical laboratoriesacross the country. With appropriate institutional advocacy, these principlescan be applied broadly to this large chemical sector.

Asarco — West Fork Biotreatment Project

Asarco has developed a biotreatment system for removing metals frommine water prior to its discharge to surface waters. Asarco’s West Fork Unitis an underground lead-zinc mine that discharges water from mine dewater-ing to the West Fork of the Black River under NPDES permit. Recentchanges in the Water Quality Standards required Asarco to explore watertreatment alternatives. Asarco initiated passive biotreatment investigations in1993 which lead to the design and construction of an anaerobic pilotbiotreatment cell (biocell) in February, 1994. The biocell (designed to treat20 gallons of water per minute) was filled with a substrate mixture of 50 per-cent old sawdust, 33 percent mine tailings, 10 percent cow manure, 5 percentalfalfa hay, and 2 percent lime rock (all material used was obtained locally;other organic materials such as yard waste and sewage sludge can be substi-tuted). Sulfate Reducing Bacteria (SRB) were cultivated within the anaerobicenvironment of the substrate. SRB are abundant in nature and are found pre-dominately in bogs and swamps. SRB produce hydrogen sulfide gas as a by-product that acts as a sulfiding agent to precipitate dissolved lead and othermetals from mine water. The pilot biocell has demonstrated continued suc-cess in reducing metals from mine water to below Missouri’s Water QualityStandards. The biotreatment cell operated efficiently through extremes ofambient temperature, water flow rates, and metal loading. Unlike conven-tional chemical water treatment plants, a biotreatment cell does not requirethe introduction of chemicals into the water, does not produce sludges on a

U.S. Department ofEnergy, Office of PollutionPrevention

U.S. Department ofEnergy, Office of EnergyResearch

U.S. Department ofEnergy, Chicago OperationsOffice

U.S. Department ofEnergy, Argonne Group

Argonne NationalLaboratory

21

daily basis that must be disposed, does not require a full time operator, is notsubject to mechanical malfunction, can operate at twice the design rate forshort periods of time without a reduction in treatment efficiency, and can beconstructed at a fraction of the cost.

The BHC Company Ibuprofen Process

A new synthetic “green chemistry” process has been developed and com-mercialized by BHC Company to manufacture ibuprofen, a well knownnon-steroidal, anti-inflammatory pharmaceutical (painkiller) marketed underthe names of AdvilTM, MotrinTM, and others. The new process involves only3 catalytic steps with approximately 80 percent atom utilization and replacestechnology with 6 stoichiometric steps and less than 40 percent atom utiliza-tion. The use of anhydrous hydrogen fluoride as both catalyst and solventoffers important advantages in reaction selectivity and waste reduction. Thischemistry (99 percent atom utilization when including the recovered by-product acetic acid) is a model of source reduction, the optimum waste min-imization method topping the Environmental Protection Agency’s wastemanagement hierarchy. Virtually all starting materials are either convertedto product, reclaimed as by-product, or are completely recovered and recy-cled in the process. The generation of waste is practically eliminated. TheBHC ibuprofen process is an innovative, efficient technology that has revo-lutionized bulk pharmaceutical manufacturing. Large volumes of aqueouswaste (salts) normally associated with such manufacturing are virtually elimi-nated. The anhydrous hydrogen fluoride catalyst/solvent is recovered and recy-cled with greater than 99.9 percent efficiency. No other solvent is needed in theprocess, simplifying product recovery and minimizing fugitive emissions. Thevirtually complete atom utilization of this streamlined process makes it truly awaste minimizing, environmentally friendly, green technology.

CleanSystem3 Gasoline

Internal combustion engines produce considerable amounts of nitrogenoxides (NOx) as a combustion by-product. Nitrogen oxides are an air pollu-tant in their own right and react with atmospheric organic compounds in thepresence of sunlight to form ozone, a powerful respiratory irritant. Despite a76 percent reduction in allowable NOx emissions from light duty gasolinevehicles over the past 25 years, U.S. motor vehicles still emit 3 million tonsof NOx each year. Source reduction in the context of vehicular NOx meansless NOx generated in the engine. Steps in this direction have been few (pri-marily exhaust gas recirculation) and, being a design feature, are not applic-able to older vehicles. There is, therefore, a genuine opportunity fortechnology which can reduce the NOx generated in vehicle engines on theroad today. Texaco has developed and introduced a patented additive tech-nology based on novel chemistry which reduces NOx formation in gasolineengines. This additive is present in all CleanSystem3 gasoline sold in theUnited States. Controlled vehicle testing has demonstrated reductions intailpipe NOx up to 22 percent. This additive fulfills the role of traditionaldeposit control (“detergent”) additives in keeping fuel system components

BHC Company (Hoechst Celanese

Corporation)

Texaco Inc.

22

Lockheed MartinTactical AircraftSystems

Rochester MidlandCorporation

clean, and provides additional performance in the area of preventing andremoving combustion chamber deposits. Cleaner combustion chambersretain less combustion heat from one engine cycle to the next, and the result-ing lower temperature leads to the formation of fewer nitrogen oxides (NOx).

Development and Implementation of Low Vapor PressureCleaning Solvent Blends and Waste Cloth Management Systems to Capture Cleaning Solvent Emissions

Lockheed Martin Tactical Aircraft Systems (LMTAS) has developed andpatented low vapor pressure organic solvents and has successfully imple-mented a low vapor pressure cleaning operations and waste cloth manage-ment and disposal system. The solvent blends and cleaning technology arebeing used by the aerospace industry, the military, and various other indus-tries. Additionally, LMTAS has substituted one of the new solvent blends(DS-104) for a CFC-113 based general purpose cleaning solvent used in thesurface wiping of aircraft parts, components, and assemblies in all aspects ofaircraft manufacturing. The substitution significantly reduced solvent useand air emissions, eliminated ozone depleting compounds from cleaningduring aircraft assembly, reduced costs, and improved chemical handlingand usage practices. From 1986-1992, LMTAS used a general purpose wipesolvent containing 85 percent CFC-113 by weight throughout the manufac-turing process. The use of the CFC-113 solvent blend resulted in the emis-sion of approximately 255 tons per year of CFC-113 and 45 tons per year ofvolatile organic compounds (VOCs). The implementation of DS-104 hasreduced wipe solvent VOC emissions to 7 tons per year in 1993 and 3 tonsper year in 1994, with no CFC emissions. Other reductions documented andinclude: 68 to 71 percent reductions in solvent use by volume, 86 to 88 per-cent savings in solvent purchase cost, and 95 to 97 percent reductions in totalair emissions.

Development of a New “Core” Line of Cleaners

Cleaning is an important practice and necessity of modern civilization.An effective cleaner must be able to penetrate through soil to disrupt/destroythe complicated types of bonding that cause it to adhere to the surface beingcleaned. Most modern cleaners are comprised of surface active agents thatare derived from petrochemical resources. While these components areeffective, they tend to be environmentally harsh and depend upon a naturalresource whose supply is finite and limited. The market for these products isestimated to be in the range of $5 billion, which equates to approximately 5billion pounds of product annually. The impact of developing chemistriesthat are less polluting during the extraction, manufacturing, use, and dispos-al of these products is therefore quite significant, as are the human health andsafety impacts. During the past few years a new family of cleaners has beendeveloped that are less toxic with reduced impacts to both people and theenvironment when compared to traditional products used for the same pur-pose. The chemistries incorporated into these products have resulted inproducts that are readily biodegradable, comprised of zero to very low

23

volatile organic components and ozone depleting substances, effective intheir intended purpose (cleaning), and economically competitive. In addi-tion, these products have low human and aquatic toxicity and low corrosiv-ity. Main molecular components of these products are derived fromrenewable, bio-based resources that are lower polluting and typically lesstoxic than their petrochemical alternatives. These new “core” line of clean-ers are an innovative approach to the formulation of an important series ofproducts and are the safest yet developed in their fields.

Development of a New Process for the Manufacture of Pharmaceuticals

In an effort to reduce the amount of waste generated at its East Hanoversite, Sandoz Pharmaceutical Corporation has evaluated all processes beingconducted at this site for their susceptibility to improvements in the utiliza-tion of solvents, to minimize the waste byproduct, and at the same timeimprove operating efficiency. One process in particular was identified thatappeared to offer significant opportunities for such process restructuring.After two years of research all the essential elements of the new process havenow been demonstrated. The new process uses a single new solvent for bothreaction medium and separation, which significantly reduces the overall sol-vent requirements and permits recycling of the used solvent by simple dis-tillation. As a result, the process waste index is reduced from the current 17.5pounds of waste generated per pound of product to 1.5, resulting in a pro-jected reduction of 170,000 pounds per year in waste generation.Furthermore, the amount of solvent used per batch is cut in half, thereby sig-nificantly reducing the usage of solvent with attendant lower risks of workerexposure and accidental releases into the environment. The decision to pro-ceed with development of a new process, despite the potential problem ofobtaining FDA approval of the process changes, is due primarily to thefavorable economics of the new process. Conservative estimates of annual sav-ings are around $775,000, compared to an investment of $2.1 million to developand implement the new process, which is equivalent to a return on investmentof 36.7 percent and less than three year pay-back time. It is estimated that over75 percent of the manufacturing savings are due to process improvements, ratherthan disposal costs of unused solvent, illustrating the process optimization bene-fits characteristic for pollution prevention innovations.

Development of a New Sealant/Adhesive Chemistry forAutomotive Windshields. A New Two Part Chemical SystemUsing Acetoacetylated Polyol Prepolymers and AminatedAcetoacetylated Polyol Prepolymers.

Up until this year all automotive windshield adhesives, used when replac-ing windshields, have been made from unblocked isocyanate prepolymers.These products may contain one to three percent isocyanates, which pose apotential severe health hazard to the workers in the manufacture of theseprepolymer adhesives. In addition to chemical workers, installers of theseproducts and car owners can be exposed to the isocyanate prepolymers,

Sandoz Pharmaceutical

Corporation

BF Goodrich

Tremco,a BF Goodrich

Company

24

U.S. Department ofEnergy

Pacific NorthwestNational Laboratory

which can pose a health risk. Tremco, a BF Goodrich Company, has beenable to develop a new sealant/adhesive chemistry that is significantly betterthan isocyanate adhesives in many respects — it demonstrates more rapidcure rate, even at low temperatures and low humidity conditions, posseshigher lap shear strengths, and is non-moisture sensitive. In addition, thisproduct is nonhazardous, nontoxic, contains no isocyanates, and poses nohealth risks to chemical workers, installers, or consumers. This new two partchemical system uses acetoacetylated polyol prepolymers. These prepoly-mers are made by reacting di and triol polymers with tert-butylacetoacetate(tBAA). Some of these acetoacetylated polyols are aminated with low mole-cular weight diamines. These acetoacetylated polyol amines are then react-ed with acetoacetylated polyols to achieve a cured polymer matrix. Thissystem produces an extremely strong isocyanate type cure and allows forfaster “drive away times” for the car owner and more productivity for theinstaller. In addition, an acetoacetylated roofing adhesive using the sametechnology is being field tested. This product is completely free of solvents,is 100 percent solid, and is environmentally friendly.

DOE Methods for Evaluating Environmental and WasteManagement Samples

“DOE Methods for Evaluating Environmental and Waste ManagementSamples (DOE Methods)” is a document that provides new technology andconsolidated methods to analytical chemistry laboratories around the countrythat are working on one of the world’s most challenging environmental issues:Cold War legacy waste. Sampling and analytical technologies that minimizewaste production have been given priority over traditional methods. It hasbeen demonstrated, for example, that some of the technologies produce 60 to70 percent less hazardous and radioactive waste than other available tech-nologies. The guidance information in “DOE Methods” also helps minimizethe number of analyses and saves time and money. Guidelines are providedon how to (1) efficiently develop a sampling and analysis program, (2) effec-tively and efficiently sample waste, (3) handle radioactive samples safely, and(4) select appropriate analytical methods. Cross references allow the users toselect from currently available standard methodologies. “DOE Methods” hasbeen available for both DOE and commercial use since 1992. It is updatedevery 6 months, thereby accelerating the release of new technology to speedEM operations. The significance of the document is in its unique applicationto the analysis of radioactive components and highly radioactive mixed waste.The document currently contains about 65 sampling and analytical methods,many of which are focused on the mixed-waste issue. The highly challengingworld of environmental problems cannot be solved without effective sam-pling and analytical methods. “DOE Methods” takes a major step in the res-olution of this problem.

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The Dow Chemical Company’s Novel INVERT TM Solvents

The industrial cleaning industry, one of the largest consumers of organicsolvents in North America, is an industry in transition. Customers, both end-users and formulators of cleaning products for the industrial cleaning indus-try, are seeking alternatives for methyl chloroform and other ozone depletingchemicals and for ways to reduce the total amount of volatile organic com-pounds (VOCs) used in their work processes. Any alternative solvents or sol-vent technology for industrial cleaners must meet specific physicalcharacteristics that result in performance properties similar to what it isreplacing. To meet industry needs, any new product should be easy to use,evaporate quickly, prevent any new health or worker safety concerns, andallow the user to meet emerging environmental regulations. INVERTTM sol-vents from the Oxygenated Solvents Business of the Dow ChemicalCompany are a remarkable advancement in solvent technology. These rev-olutionary new products maintain the performance properties of organic sol-vents but incorporate the environmental benefits of water. INVERTTM

solvents are best described as the first practical development of solvent con-tinuous microemulsions that can function as an alternative to traditional sol-vents. The unique properties of microemulsions have led to their use in adiverse range of applications that include enhanced oil recovery, environ-mental remediation, consumer products, pharmaceutical formulations andmedia for polymerization.

DryWashTM

All conventional dry-cleaning solvents present health risks, safety risks, orare detrimental to the environment. Currently, the dry-cleaning industryuses perchloroethylene (85 percent), petroleum based or Stoddard solvents(12 percent), CFC-113 (less than two percent), and 1,1,1-trichloroethane.Perchloroethylene is a suspected carcinogen; petroleum based solvents areflammable and smog producing; and CFC-113 is an ozone depletor and tar-geted to be phased out by the end of 1995. Health risks due to exposure tothese cleaning solvents and the high costs of implementing and complyingwith safety and environmental restrictions and regulations, reduced dry-cleaning profit margins. Solvents are suspected of contaminating groundwater, air, and food products. For these reasons, the dry-cleaning industry isengaged in an ongoing search for alternative, safe and environmentallyfriendly cleaning technologies, substitute solvents, and methods to controlexposure to dry cleaning chemicals. DryWashTM, a Hughes carbon dioxidetechnology, has been developed and marketed as a safe, ecologically accept-able and cost effective alternative to the current dry-cleaning process.Carbon dioxide is a readily available, inexpensive, and unlimited naturalresource. It is chemically stable, non-corrosive, non-flammable, non-ozonedepleting and non-smog producing. The DryWashTM system reuses a natu-rally occurring by-product with a multitude of sources. A dry-cleaning devel-opmental prototype using liquid carbon dioxide has been built anddemonstrated. Completion of a 10 kilogram commercial size cleaning unit isexpected during the first quarter of 1996.

The Dow ChemicalCompany

Hughes Environmental

Systems, Inc.

26

DuPont Company The DuCare “Zero Effluent” Recycle Chemistry System

The Printing and publishing pre-press industry is undergoing a revolu-tionary change driven by advances in imaging technology from a craft-basedindustry to one relying far more on digital imaging and printing technology.From a user perspective, this new technology is more environmentallybenign than the process it replaces. Several iterations of improvements inhardware and software will be required before digital imaging completelyreplaces conventional chemical imaging. The DUCARE system is a “bridge”between the current and developing systems. It is designed as a “drop in” forconventional processing and enables the customer to continue utilizing theircurrent equipment, thus avoiding a financial burden while still eliminatingthe adverse environmental impact. DUCARE is an environmentally proac-tive way for customers to prevent any film processor effluent from goingdown their drain. Typically customers discharge the effluent to the drain, payto have it hauled away and disposed, or use expensive high maintenanceequipment for on-site treatment. The effluent contains hazardous chemicals(as defined by SARA Title III), very high BOD and COD, high silver andpH extremes. DUCARE, offered only by DuPont, solves these problemsusing several industry firsts. A new developer was invented which has noSARA Title III chemicals and is based on a vitamin C isomer. The chemistryis designed to use 25 to 40 percent less product than conventional chemistryand is recycled at its manufacturing sites to insure high quality and “likenew” performance. The wash-water recirculating unit reduces water use upto 99 percent. This system can be used worldwide, wherever a cost effectivereverse distribution system can be set up.

The ECO Funnel

The ECO Funnel and Container is a new product designed to preventvolatile toxic air contaminants from evaporating into the laboratory workenvironment and into the atmosphere through the laboratory fume hood sys-tem. Typically, a simple funnel is used in pouring waste solvent into a wastebottle or carboy. In most cases the funnel is left on top of the bottle perma-nently during the day, resulting in significant emission due to evaporation ofvolatile organic compounds (VOCs) from the bottle into the laboratory envi-ronment or fume hood. It may seem that contamination of the atmospherefrom such sources may not be large enough to be important or significant;however, exact measurements have proven the contrary. For example, an 8liter carboy filled with 8 liters of dichloromethane will emit 500 mL (1.5pounds) of this solvent into the atmosphere in 5 days. The emission will varydepending on the type of solvents used. The fume hood face velocity alsocan affect the evaporation rate. However, for a typical fume hood at 700cubic feet per minute and a typical 4 liter waste bottle with a regular funnelcontaining 1000 mL tetrahydrofuran, 1000 mL acetone, and 1500 mLdichloromethane, the emission rate was 0.09 pounds per 8 hours or 33pounds per year. California-Pacific Lab and Consulting designed and patent-ed a new funnel that has a lid connected to a shut-off ball which double sealsthe system. The funnel stem is also longer and sealed to the bottle cap inorder to prevent emission from the side of the stem. Under the same condi-

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tions as described above for the 4 liter waste bottle with a standard funnel,the ECO Funnel and Container resulted in zero emissions.

Elimination of Ozone-Depleting Chemicals in the Printed WireBoard and Electronic Assembly and Test Processes

IBM Austin is a manufacturing and development facility. Operationsinclude the manufacture of printed wiring board (PWB) in the Panel Plantfacility and electronic circuit cards in the Electronic Card Assembly and Test(ECAT) facility. In 1992 IBM Austin completely eliminated the use of CFCsand other ozone depleting substances from its PWB and ECAT processes.This elimination program resulted in 100 percent reduction of CFC-113(1988 peak usage of approximately 432,000 pounds) and 100 percent reduc-tion of methyl chloroform (1988 peak usage of approximately 308,000pounds) from IBM Austin’s PWB and ECAT processes. These accomplish-ments were achieved by converting to an aqueous-based photolithographicprocess in the PWB facility in 1989, an interim aqueous cleaning process inthe ECAT facility in 1991 and 1992, and a final No-Clean process (eliminat-ing the aqueous cleaning process) in the ECAT facility. Changing from a sol-vent-based photolithographic process to an aqueous-based processeliminated methyl chloroform (MCF) from PWB panel manufacturing (1988usage of 181,000 pounds). The interim process changes to aqueous cleaningeliminated MCF from manufacturing processes in ECAT (1989 peak usageof 196,000 pounds) and were largely responsible for eliminating CFC-113from all manufacturing processes at the IBM site. Although CFC-113 waseliminated from the site in 1991 and MCF was eliminated in 1992, ECAT’sultimate goal was to convert all ECAT processes to No-Clean manufacturingprocesses. This conversion was completed in 1993.

The Emission Quantification Model

In the semiconductor manufacturing process, liquid and gaseous chemi-cal mixtures are used to manufacture submicron devices. These chemicalsare categorized into four general groups: corrosives, organics, toxics, and flu-orinated compounds. Local, state, and federal environmental regulationsgoverning these materials are becoming more stringent and facilities mustensure protection of human health and the environment. To help accomplishthis, ADM developed the Emissions Quantification Model (EQM) as amethod to identify and quantify the chemicals used in manufacturingprocesses and incorporate them into a comprehensive environmental man-agement system. Based on a modified mass balance model, pollution pre-vention and control outcomes were used to develop a real-timemeasurement method. The EQM provides information such as toxicity,usage, and emission rates and is an invaluable tool for assessing humanhealth and environmental impacts as well as identifying opportunities tooptimize, reduce, reuse, recycle, and eliminate chemicals. The EQM has ini-tiated many improvements at AMD’s Austin site. For example, chemicalswith potential teratogenic properties were identified and replaced with lesstoxic chemicals that still meet the specifications required to produce semi-conductors. Methyl ethyl ketone, a hazardous air pollutant as well as a SARA

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313 reportable chemical, was replaced by methyl propyl ketone, a much lesshazardous substitute. Data from the EQM assessments identified chemicalsused in large quantities, including sulfuric acid and isopropyl alcohol, thatcould be recycled. Currently, ADM is recycling 50 percent of the sulfuricacid used in these facilities and is evaluating isopropyl alcohol recycling. Inthe near future, all sulfuric acid used in these facilities will be recycled, andif the capital expenditure is justified, feasible, and approved, isopropyl alco-hol reprocessing will be implemented.

Environmentally-Driven Preparation of Insensitive Energetic Materials

An innovative approach has been developed at Lawrence LivermoreNational Laboratory to the synthesize 1,3,5-triamino-2,4,6-trinitrobenzene(TATB) and other insensitive energetic materials through the use of VicariousNucleophilic Substitution chemistry (VNS). TATB is a reasonably powerfulinsensitive high explosive (IHE) whose thermal and shock stability is consid-erably greater than that of any other known material of comparable energy.The high cost of TATB ($100 per pound) has precluded its use for civilianapplications such as deep-hole oil explorations. TATB is manufactured in theUnited States by nitration of the relatively expensive and domesticallyunavailable 1,3,5-trichlorobenzene (TCB) to give 2,4,6-trichloro-1,3,5-trini-trobenzene (TCTNB) which is then aminated to yield TATB. The new VNSmethod developed at Lawrence Livermore National Laboratory for the syn-thesis of TATB has many “environmentally friendly” advantages over the cur-rent method of synthesis of TATB. Most significantly, it allows the eliminationof chlorinated species from the synthesis of insensitive energetic materials.The new synthesis of TATB uses unsymmetrical dimethylhydrazine(UDMH), a surplus propellant from the former Soviet Union, and ammoni-um picrate (Explosive D), a high explosive, as starting materials in lieu of thechlorinated species, TCB. Several million pounds of Explosive D are targetedfor disposal in the United States; 30,000 metric tons of UDMH also await dis-posal in a safe and environmentally responsible manner. The use of these sur-plus energetic materials as a feedstocks in the new VNS method ofsynthesizing TATB allows an improved method of demilitarization of con-ventional munitions that also should offer significant savings in productionthereby making this IHE more accessible for civilian applications.

The INFINITY Dyeing Process

The INFINITY dyeing process was developed as an alternative methodto manage the dyeing cycle for nylon textiles. Over 8 billion pounds of nylontextiles are consumed each year, and most are dyed to meet aesthetic andfunctional demands. In the United States alone, consumption of dyes fornylon exceeds 30 million pounds, much of which is left in the spent dye bathafter the fabric is dyed. This waste must be treated to avoid pollution ofdownstream waterways. Mills are meeting regulatory requirements throughconventional process control techniques and end of pipe treatment. TheINFINITY dyeing process lets mills reduce their consumption of dyes andother chemicals by 25 percent, and in some applications, water and steam

U.S. Department ofDefense, Office of Munitions

U.S. Department ofEnergy, Weapons SupportedResearch

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use per dye cycle is cut in half. Conventional methods use up to 4,000 gal-lons of water, 20 pounds of dye and 10 pounds of dye assist chemicals per1,000 pounds of fabric. The INFINITY dyeing process uses only 75 percentof the dye previously required, half the water, and less dye assist chemicalsto get the same fabric color. In addition, dye discharge into mill effluentstreams can be reduced as much as tenfold. A mill with a 90 percent exhaustrate may discharge 500 pounds of unused dye into the mill’s wastewatertreatment stream each week. With INFINITY, the same mill can move to 99percent exhaust, reducing the amount of dye discharged to 50 pounds perweek; a significant step toward attacking waste at the source. The process iscurrently being used at nylon textile mills in the United States, and work hasbegun on the feasibility of using the process on wool, cotton, and polyesterblend fabrics. Cost savings by most mills using this process could easilyexceed $100,000 per year.

Innovative Techniques for Chemical and Waste Reductions in thePrinted Wire Board Circuitize Process

IBM produces 1.7 million square feet of multi-layer circuit boards peryear in a manufacturing plant in north Austin. Aqueous chemical baths andrinse water are processed at a pretreatment plant where acidity is neutralizedand dissolved copper is removed prior to discharge to a sanitary sewer forfurther treatment in a POTW. In 1991, the treatment process produced 1,417tons of metal hydroxide sludge, a RCRA F006 hazardous waste. In 1992, ateam of environmental engineers, manufacturing engineers, and laboratorypersonnel was formed to reduce hazardous waste sludge generation at thewater treatment plant by minimizing waste generation in the imaging line.Two areas were identified for their waste minimization potential: acid usedin cleaning operations and developing solutions used prior to etching opera-tions. Minimizing acid in the waste water reduces the amount of lime need-ed to neutralize the solution and reducing developing solution reduces thecarbonates in the waste water which precipitates as calcium carbonate in thepresence of lime. By 1994, the team accomplished a 90 percent reduction inhydrochloric acid used in cleaning for an annual savings of approximately$340,000 in chemical cost. Additional work allowed for a 40 percent reduc-tion of developing and stripping solutions used in the imaging area, for anannual savings of approximately $75,000. These changes resulted in anapproximately 75 percent decrease in use of lime at the pretreatment plant.This decrease in combination with reduced carbonate usage in developingsolutions resulted in a decrease in sludge production of over 670 tons peryear (based on first half 1994 results), a 47 percent reduction from 1991sludge generation, for an additional savings of $250,000 in sludge disposalcosts. This project has shown that waste minimization through chemicalsource reduction can reduce expenses as well as reduce waste.

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Invention and Commercialization of CONFIRM TM SelectiveCaterpillar Control Agent

CONFIRMTM is a breakthrough in caterpillar control. It is chemically,biologically, and mechanistically novel. It effectively and selectively controlsimportant caterpillar pests in agriculture without posing significant risk to theapplicator, the consumer, or the ecosystem. It will replace many older, lesseffective, more hazardous insecticides. CONFIRMTM received full registra-tion in the United States for codling moth control in walnuts in early 1995and was used effectively in 1994/5, under emergency exemption, to combatsevere beet armyworm outbreaks in cotton and vegetables in several south-ern states. CONFIRMTM insecticide controls caterpillars through an entirelynew and inherently safer mode of action than current insecticides. It acts bystrongly mimicking a natural substance found in the caterpillar’s body, called20-hydroxy ecdysone, which is the natural “trigger” that induces molting andregulates development in insects. CONFIRMTM disrupts the molting processin caterpillar pests, causing them to stop feeding within hours of exposureand to die soon thereafter. Although CONFIRMTM is a potent mimic of 20-hydroxy ecdysone in caterpillars, it is a surprisingly poor mimic in mostother insects and arthropods, and therefore is remarkably safe to a widerange of key beneficial, predatory, and parasitic insects such as honeybees,ladybeetles, parasitic wasps, predatory bugs and lacewings. In addition to itsnovel and selective mode of action, CONFIRMTM does not bioaccumulate,volatilize, leach, or persist unreasonably long in the environment. All ofthese reasons make CONFIRMTM one of safest, most selective, and most use-ful caterpillar control agents ever discovered.

Liquid Oxidation Reactor

Praxair has developed a unique process that allows the safe oxidation oforganic chemicals with pure or nearly pure oxygen. This technology, knownas the Liquid Oxidation Reactor (LOR) provides significant environmentaladvantages compared to conventional, air-based oxidation processes. Theuse of oxygen in place of air reduces the total gas throughput to the reactor,thereby reducing the compression energy and the amount of vent gas thatmust be treated prior to atmospheric release. In addition, the oxygen use canpositively affect the chemistry of the reaction, allowing the operation of theprocess at lower temperatures and/or pressures, thereby improving selectiv-ity without sacrificing production rate. The use of the Praxair LOR increas-es the overall rate of reaction and volumetric productivity of hydrocarbonoxidations while increasing selectivity and reducing the loss of solvent andreactant to carbon oxides. The increased chemical efficiency with oxygenresults in substantial raw materials cost saving, and a 96 percent reduction inthe quantity of waste gases. The cost of product purification and waste dis-posal is reduced substantially. In addition, the lower temperature operationsafforded by the LOR process reduces the loss of reactant and/or solvent toby-products and to waste streams that also can contribute to environmentalproblems and must be treated prior to release. The LOR will enable a largeand important segment of the U.S. chemical industry to realize more efficientuse of raw materials, reduced environmental emissions, and energy savings.

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Because the LOR also allows for higher productivity, lower capital costs,and, consequently, improves competitiveness, there are significant incentivesfor the implementation of the technology. Average operating-cost savingsand productivity gains worth $5-$20 million per plant per year have beenprojected

Magnetic Separation for Treatment of Radioactive Liquid Waste

High Gradient Magnetic Separation (HGMS) is the application of intensemagnetic fields to selectively separate solids from other solids, liquids, orgases. The HGMS process has demonstrated promise for treatment of wastestreams containing actinide at Los Alamos National Laboratory (LANL).The caustic liquid waste generated by operations in the LANL PlutoniumProcessing Facility (TA-55) can produce up to 30,000 L of liquid effluentannually, with an average alpha activity of 1010 dpm/L. Treatment and dis-posal of the liquid effluents at the LANL Waste Water Treatment Facility(TA-50) can ultimately produce up to 15 tons of TRU solid waste per year.In order to avoid the TA-50 treatment, the goal at TA-55 is to reduce theradioactivity in the waste streams to less than 5.8 x 105 dpm/L. Physical sep-aration processes, such as HGMS, are particularly attractive because noadditional waste is generated during processing. HGMS is capable of con-centrating the actinides in process waste streams to form a low volume,actinide-rich stream for recycling, and a high-volume, actinide-lean streamfor direct discard. The proposed technology has been demonstrated success-fully on a laboratory scale at TA-55 where results from screening experi-ments on radioactive caustic liquid waste water indicate that over 99.9percent extraction of Pu activity can be achieved using HGMS (representsdecontamination levels of three orders of magnitude to about 4.4 x 105

dpm/L). The application of this technology to radioactive liquid waste efflu-ents would eliminate radioactivity from the source, in addition reducing thevolume of transuranic solid waste that is produced with the current treatmenttechnologies. The hazard of pumping radioactive liquid waste to offsite facil-ities would also be eliminated because treatment of TA-55 effluent wouldoccur prior to transportation.

A Microwave Oven Dissolution Procedure for a Ten Gram Sampleof Soil Requiring Radiochemical Analysis

A microwave soil dissolution procedure was incorporated into a standardanalytical method for testing soils for americium and plutonium. This modi-fication displaces several hot plate dissolution steps by incorporating amicrowave oven with new commercially available products. The new pro-cedure uses a commercially available microwave oven that has the capabili-ty to monitor and control the pressure and temperature of a control vesselusing a feed back system. The ability to repeatedly obtain and controldesired temperatures and pressures has resulted in improved analytical pre-cision because the reaction conditions can be reproduced. This new proce-dure also reduces the consumption of hazardous substances, the amount of

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air pollution produced, worker exposure to hazardous substances, and sam-ple preparation time. The use of closed vessels in this modified procedurealso results in reduced hazardous reagents use. Less reagents means less haz-ardous waste and air pollution are produced, and reduced worker exposureto the reagents. In addition, the use of the microwave oven reduces the timerequirements from two to three days for the hot plate procedure to eighthours.

NAFION Membrane Technology

Membrane technology is now recognized as the state-of-the-art for chlo-ralkali chemical production, which constitute the second largest commoditychemical volume produced globally. NAFION membranes are acknowl-edged as the world leader in bringing about a technology “revolution,” whichhas made the membrane electrolyzer system the technology of choice overthe incumbent mercury amalgam cells and asbestos diaphragm electrolyzers.While significantly reducing the environmental impact of the old technolo-gies, membrane systems confer the advantages of a new electrolysis processwith lower investment and lower operating costs. Before NAFION andmembrane technology, the production of chloralkali chemicals was depen-dent on either mercury amalgam cells or asbestos diaphragm systems. Whilethese systems may be operated safely, they pose health and environmentalconcerns in use and disposal. Membranes, such as NAFION, now offer amore environmentally-friendly and economically attractive alternative,which accounts for the rapid global adoption of membrane technology.Another rapidly emerging application of NAFION is in the area of alterna-tive energy, where electricity is produced from the “combustionless burning”of hydrogen with oxygen in air via a membrane fuel cell. Fuel cell technolo-gy, with hydrogen as a fuel, is pollution-free. NAFION membranes often arecited in the many commercial developments of membrane fuel cell systems.As membrane fuel cells mature in the commercial mass market, more glob-al energy needs will be served by renewable, sustainable, and environmen-tally-friendly sources of power.

Nalco Fuel Tech NOxOUT ® Process

Nalco Fuel Tech is a joint venture of Nalco Chemical Company and FuelTech formed to develop and market air pollution control technologies. NalcoFuel Tech’s flagship technology, NOxOUT®, selectively reduces harmfulnitric oxide emissions from the flue gases of stationary combustion sourcesto yield nitrogen gas and water, leaving no solid residue requiring disposal.The NOxOUT® Process meets many of today’s environmental challengessuch as employing less toxic chemistries, reducing or eliminating toxicreleases to the environment, converting wastes to more environmentallyacceptable discharges, and by using these chemistries, enables reduced ener-gy consumption. The NOxOUT® Process provides an economical solutionfor meeting the stringent regulatory requirements for NOx reduction fromfossil fuel and waste fuel combustion sources. NOxOUT® is capable of pro-viding up to 75 percent reduction of NOx emissions (existing combustion

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modification such as low NOx burners, flue gas recirculation, and overfire airare effective, yet normally only provide NOx reductions in the range of 20 to50 percent). The process uses chemicals and sophisticated injection equip-ment to convert NOx to harmless species — nitrogen and water. In theNOxOUT® Process, an aqueous solution of proprietary chemicals is intro-duced into the flue gas of the combustion equipment. The program isdesigned according to the type, size, and operating load of the boiler, andNOx reduction required. The NOxOUT® Process is being used commercial-ly and has been demonstrated in tests on a wide range of combustionprocesses and fuels. The process is well-suited to new combustion units of allsizes — from small industrial units to large utility installations. In addition, thesystem can be retrofitted to most existing units. The environmental benefitsare: high NOx reduction, no disposal by-products, no SARA Title III chem-ical reporting requirements, and increased energy efficiency due to the lowcost per ton to remove NOx.

Nalco NALMET ®

New, stricter NPDES discharge limits for effluent metals are impactingboth metal and non-metal industries. Stringent NPDES plant effluent metalconcentration limits focus on effluent toxicity reductions that impact bothmetal and non-metal industries. Traditional metal removal programs usemultiple chemicals and toxic components such as dialkyldithiocarbamates,sodium sulfide, and ferrous sulfide. In addition, the concentration limits forheavy metals such as copper, lead, nickel and zinc often cannot be met bytraditional metal precipitation processes. Nalco Chemical Company devel-oped NALMET®, a patented, low-toxicity program for metal removal thatincludes a liquid polymer containing a metal chelating functional group thatsimultaneously precipitates metals and clarifies the waste stream. It is effec-tive on soluble, mixed metal wastes and in many cases, reduces final sludgevolumes by 30 to 75 percent. NALMET® also allows some RCRA hazardoussludges to be reclassified as non-hazardous. Automated chemical feed withpatented sensor technology makes the NALMET® program easier to use,substantially decreases product overfeed, and assists with waste minimiza-tion. More significantly, this product offers a remedy to environmental man-agement problems by helping Nalco customers consistently meet theirextremely low NPDES metals discharge limits. NALMET® offers a realisticapproach to “green” chemistry because the technology is based on high mol-ecular weight polymers that express low toxicity, is easy to implement, doesnot require extensive changes in plant design or capital investment, and isbroadly applicable and readily transferrable to other industry sectors.

Nalco PORTA-FEED® Advanced Chemical Handling Systems

Nalco Chemical Company is a manufacturer and marketer of specialtychemicals for industrial water treatment and process applications. In theearly 1980s, drum disposal and the associated chemical residue was becom-ing a health and environmental risk for Nalco customers and the generalpublic. In response, Nalco developed the PORTA-FEED® AdvancedChemical Handling System consisting of returnable containers to help

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reduce chemical waste and the potential risks associated with non-returnabledrums. The Nalco PORTA-FEED® System has more than 96,000 returnable,stainless steel containers of various sizes, ranging from 15 gallons to 800 gal-lons to accommodate all Nalco customers and applications. It is the largestfleet of returnable chemical containers in the world. All the units are owned,tracked and maintained by Nalco as a cradle-to-grave risk managementprocess. Since it began, the PORTA-FEED® pollution prevention programhas helped Nalco customers eliminate the need to dispose more than threemillion drums and more than 30 million pounds of chemical waste. In 1985,33 percent of the Company’s annual sales were shipped in non-returnabledrums and required 500,000 drums. Ten years later, only 7 percent of salesare shipped in non-returnable drums and the number of drums has beenreduced 80 percent. By the year 2000, Nalco expects to have eliminated theneed to dispose of 10 million drums and 100 million pounds of chemicalwaste worldwide as a result of the PORTA-FEED® program. ThePORTA-FEED® System provides several benefits both to users of Nalcochemicals and to the environment, which includes eliminating drums, theassociated residual chemicals, and long-term environmental risk; reducingthe likelihood of spills, leaks, and container damage during transportationand use; simplifying chemical handling, which enhances worker safety byreducing exposure; and reducing the need for on-site chemical inventoryand chemical storage.

Nalco TRASAR® Technology

Nalco Chemical Company is the largest water treatment specialty chemi-cal company in the world. Customers range from water treatment plants inlarge industrial complexes that produce commodities such as steel, electrici-ty, paper, gasoline, and fertilizer to smaller water facilities in hotels, hospi-tals, breweries, canneries, and public sewage treatment facilities. Nalcoprograms such as TRASAR® Technology, Diagnostic TRASAR®, andTRA-CIDETM are impacting the way the world manages water by helpingcustomers reduce pollution at its source and conserving energy. These appli-cations are a complete cradle-to-grave approach to water management.TRASAR® Technology has several aspects that can be grouped in “stages”for discussion. In stage I, an inert fluorescent material “trace” is blended intoTRASAR® treatment products. The signal from the “trace” is used to controlthe treatment chemical application and injection rate changes are madeinstantaneously and automatically. It is common to see a 20 to 30 percentreduction in total chemicals used when customers convert to a TRASAR®

program. Stage II of TRASAR® Technology relies on the direct, automaticdetection of the treatment chemical. Where stage I might be analogous toadding microscopic, glowing ping-pong balls to the chemical product, stageII is like putting a bar code on the active ingredient molecule. Nalco hastaken fluorescent materials and chemically bonded them to the active ingre-dients. Stage II TRASAR® Technology allows Nalco to correlate variationsin the consumption of the chemical with variations in the way the water sys-tem is operated. Stage III TRASAR® Technology is based on performance(e.g. corrosion protection, prevent foaming, etc.). Nalco monitors how wellits products inhibit corrosion, disperse suspended solids, and prevent foam-ing. The dosage is further adjusted based on the performance measures.

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Nalco ULTIMERTM Polymer Technology

Most industrial processes use water as a raw material or as a processingaid. Typically, water taken from the environment must be conditioned toremove suspended solids, organic matter, and other materials that may beharmful to the industrial process before it is used. Water that has been usedin industrial processes often must be treated to remove harmful wastes andcontaminants before being reintroduced to the environment. Solids/liquidsseparation unit operations are critical to cost-effective and safe operation ofmost industrial operations. High molecular weight, water-soluble polyacry-lamides are commonly used to assist solids/liquids separation in many indus-trial water and waste treatment applications. In 1995, shipments ofpolyacrylamides in the United States are expected to be over 200 millionpounds. Worldwide, the market for polyacrylamides is presently at least onebillion dollars. As flocculants, these polyacrylamides are extremely effective.The last major technical improvement in flocculant technology might beconsidered the invention and development of inverse emulsion polymers byNalco Chemical Company in the late 1970’s. In 1995, Nalco continued itstechnological innovation in this area by introducing the first major innova-tion in water treatment flocculants since the development of inverse emul-sion cationic polyacrylamides—ULTIMERTM polymers. ULTIMERTM

polymers are a new product line of high molecular weight cationic poly-acrylamides that are formulated without oils or surfactants. ULTIMERTM

Polymer technology is more effective in purifying industrial processes andwastewater than traditional technology and eliminates toxic components andhas worldwide applicability in all industrial nations. Its toxic use reductionand pollution prevention is achieved by eliminating environmental dis-charges that present environmental hazards.

New Catalyst for Producing ULTEM ® Thermoplastic Resin

GE Plastics produces an engineering thermoplastic known as ULTEM®

polyetherimide resin. The production of this resin involves several compli-cated synthetic conversions and generates both an aqueous waste streamcontaining organic materials and an organic waste stream. The key step inthe process depends on a catalyst that has been a research “target of oppor-tunity” for several years. Laboratory studies indicated that the amount ofwaste generated from this step could be significantly reduced using severalmembers of a new catalyst class. A small plant trial verified the early find-ings. In 1995, the most promising member of this new catalyst class wasstreamlined, and a full plant trial was conducted in the ULTEM® manufac-turing plant. Based on the full plant trial, the following pollution preventionbenefits were demonstrated: the volume of organic waste stream for off-sitedisposal was reduced by 90 percent or 123,000 pounds a year; the water-based organic waste for on-site thermal oxidization was reduced by 60 per-cent or 300,000 pounds a year; 50 percent less catalyst was consumed due togreater effectiveness per pound of catalyst; the amount of waste from themanufacture of the catalyst itself was reduced by 75 percent or 39,000pounds a year; the amount of energy required to produce each pound of theresin was reduced by 25 percent or 5 x 109 BTU/yr; and the amount of aworkplace hazardous by-product was reduced by 90 percent. In addition to

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these health and environmental benefits, the new catalyst system also offersseveral significant economic advantages. This catalyst technology is the cor-nerstone of new process chemistry for manufacturing the ULTEM® resin thatwill eliminate completely the need for a thermal oxidizer.

No-Clean Soldering

CTS Corporation Resistor Networks produces solid ceramic resistor net-works in various single in-line, dual in-line, surface mount, and through-holepackages with standard or custom circuit designs. Soldering operations werea major source of hazardous waste generation at CTS’s Berne facility. Oil ontop of the solder, flux, and cleaning solvents to remove the oil after solder-ing, generated large quantities of hazardous waste. A solder process, new toCTS, was developed and implemented on all manufacturing lines. The No-Clean soldering process was implemented in March of 1993 and eliminatedthe use of wave oil, soldering fluxes, and cleaning solvent. Changing to a No-Clean soldering process involved installing hoods with an inert atmosphereover the solder pots, which eliminated the need for oil and flux. The partsare clean after solder and thus no solvent cleaning is needed. In 1992, wastegenerated from CTS’s soldering operations included 21,767 pounds of waveoil; 15,792 pounds of flux; 9,900 pounds of 1,1,1-trichloroethane solvent(TCA); and 226,000 pounds of 1,1,2-trichloroethylene solvent (TCE). In1995, waste oil, flux, TCA, and TCE from soldering operations was com-pletely eliminated. The elimination of solvent-based cleaning operations alsohas resulted in a reduction in air emissions from 1992 levels of 99,000pounds per year of TCA and 250,000 pounds per year to zero (estimated for1996). By eliminating these chemicals from soldering operations, the hazardsfrom releasing these chemicals to the environment is eliminated and work-ers are no longer exposed to fumes from fluxes, oils, and cleaning solventsthat are typical of the solvent-based soldering operations. In addition, theproduct quality has improved.

Non-Cyanide Silver Electroplating

A proprietary, non-cyanide silver electroplating process, Techni-SilverCy-Less L, was developed by Technic. Cyanide based processes for electro-plating have been extensively used in the United States for the last fifty years.Due to the hazardous nature of cyanide, extensive safety precautions must beincorporated when manufacturing electroplating chemicals, transporting thesolutions to user sites, using the electroplating process, and disposing wastesolutions. For example, if cyanide based solutions become too acidic, largeamounts of poisonous cyanide gas are created. Historically, the electroplatingindustry has suffered many accidents due to the use of cyanide and on a fewoccasions have resulted in death. Alternatives to cyanide-based solutions hadbeen developed for all metals commercially electroplated except silver. Thenon-cyanide silver electroplating process developed by Technic provides analternative that is noticeably less toxic than the cyanide process and one that isinherently safer with regard to accident potential. In addition, tests clearlyshow that the non-cyanide formulation is capable of producing sound, thick(around 125 µm) silver deposits that are extremely fine-grained and exhibit

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properties comparable to those produced in silver cyanide formulations. Withthe success of the non-cyanide chemistry, Technic has made it possible to oper-ate an entire plating facility without having to use any cyanide compounds.

Polycarbonate/Polydimethylsiloxane Copolymers for Thermal Print Media

The process to make polycarbonates using bischloroformates and bisphe-nols or diols was developed and commercialized in the early 1990’s by thePolymer Products Unit of the Eastman Kodak Company in Rochester, NewYork. The original process to produce the polycarbonate of bisphenol A,diethylene glycol, and bisaminopropyl polydimethyl-siloxane was developedin 1992 and commercialized in 1993 for use in a new Thermal Print Mediaproduct. Concerns over waste and air emissions, as well as cost and capacityissues, prompted a research and development effort to replace this polymerbefore production volumes increased to forecasted high levels. The newprocess to produce a similar polycarbonate/polydimethylsiloxane copolymerwas certified early in 1994. Improvements include the following: (1) the newprocess is made in the solvent in which the polymer is coated, and is deliv-ered to the manufacturing department dissolved in that solvent, eliminatingthe methanol precipitation, methanol washing, and vacuum drying steps; (2)in the new process, triethylamine is used as the acid acceptor instead of pyri-dine, making the water wash waste streams less hazardous; (3) the newprocess uses the commercially available diethylene glycol bischloroformate,eliminating the need to manufacture the bisphenol A bischloroformate atKodak in Rochester (the bisphenol A bischloroformate synthesis uses phos-gene as a key reactant, and its purification produces large quantities of haz-ardous waste containing heptane and silica gel). The new process will yieldover 1.2 million pounds of hazardous waste reductions and more than 3,000pounds of air emissions reductions from 1994 to year end 1996.

The Removal of Oxides of Nitrogen by In Situ Addition ofHydrogen Peroxide to a Metal Dissolving Process

An innovative technology for the removal of oxides of nitrogen (NOx) ina metal dissolving process by adding hydrogen peroxide was developed andimplemented by Mallinckrodt. Salts are produced by dissolving metals innitric acid and during the dissolving process, approximately 30 tons per yearof NOx emissions are generated. A study was completed to determine thebest method for reducing NOx emissions from the process. While the litera-ture suggests that NOx is required to catalyze the dissolution reaction, thistheory was challenged and it was proposed to oxidize the NOx back to nitricacid by adding hydrogen peroxide directly to the process. Trial runs usingthis technology were completed and resulted in complete elimination of NOx

emissions. The full scale hydrogen peroxide addition process has eliminatedthe generation and evolution of approximately 30 tons per year of gaseousNOx waste, while at the same time reducing nitric acid usage by approxi-mately 109 tons per year. Further, approximately 13 million gallons of scrub-ber waste water were eliminated annually since the scrubber, traditionally

Eastman KodakCompany

Mallinckrodt Chemical, Inc.

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used by the chemical industry to control the NOx that is generated andreleased from reactions, is no longer needed. This technology can be used byany process in any industry that generates NOx emissions when dissolvingmetals in nitric acid or pickling metals using nitric acid.

Roundup ReadyTM Technology

The Roundup ReadyTM Technology is the mechanism by which cropselectivity to Roundup®, the world’s largest selling herbicide, has been intro-duced into crop plants. The technology is the result of the discovery of aunique set of genes and the introduction of these Roundup ReadyTM genesinto crop plants. These genes were identified following many years ofresearch on the mode of action and environmental fate of the active ingredi-ent of the Roundup® herbicide. The Roundup ReadyTM Technology genesprotect the crop plant from damage by inserting a new version of theenzyme, which is normally inhibited by the herbicide, so that the enzyme isnow insensitive to the herbicide. In addition, the Roundup ReadyTM

Technology provides a mechanism for the plant to degrade the herbicidetaken into the plant. Initial commercial launch will be in soybean, cotton,and corn in the United States in the 1996-1998 time frame. The technologyis widely applicable to other crops. Potential applications include wheat, rice,forestry, and vegetable and salad crops. This technology extends to a wideraspect of agriculture and food production, the ability to use one of the mostbeneficial and environmentally benign farm chemicals ever discovered. Theimpacts will be seen in the shift in the spectrum of herbicides possible for in-crop use. Farmers who plant Roundup ReadyTM soybeans in 1996, for exam-ple, will be able to reduce herbicide use in those soybean fields by up toone-third and still control weeds better. In addition, Roundup ReadyTM tech-nology is compatible with no-till crop production, a practice that is expand-ing in the United States and around the world.

Solvent Replacement and Improved Selectivity in AsymmetricCatalysis Using Supercritical Carbon Dioxide

The use of supercritical carbon dioxide as a substitute for organic solventsalready represents an important tool for waste reduction in the chemicalindustry and related areas. Coffee decaffeination, hops extraction, and essen-tial oil production as well as waste extraction/recycling and a number of ana-lytical procedures already use this nontoxic, nonflammable, renewable, andinexpensive compound as a solvent. The extension of this approach to chem-ical production, using CO2 as a reaction medium, is a promising approach topollution prevention. Of the wide range supercritical carbon dioxide reac-tions that have been explored, one class of reactions has shown exceptionalpromise. Los Alamos National Laboratory has found that asymmetric cat-alytic reductions, particularly hydrogenations and hydrogen transfer reac-tions, can be carried out in supercritical carbon dioxide with selectivitiescomparable or superior to those observed in conventional organic solvents.Los Alamos has discovered, for example, that asymmetric hydrogen transferreduction of enamides using ruthenium catalysts proceeds with enantiose-lectivities that exceed those in conventional solvents. The success of asym-

Monsanto Company

Los Alamos NationalLaboratory

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metric catalytic reductions in CO2 is due in part to several unique propertiesof CO2 including tuneable solvent strength, gas miscibility, high diffusivity,and ease of separation. In addition, the insolubility of salts, a significant lim-itation of CO2 as a reaction solvent, has been overcome by using lipophilicanions, particularly tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (BARF).These discoveries demonstrate an environmentally benign and potentiallyeconomically viable alternative for the synthesis of a wide range of specialtychemicals such as pharmaceuticals and agrochemicals.

Stepan Company PA Lites Polyester Polyol

Stepan Company’s Polyester Polyol product, manufactured using thePhthalic Anhydride Process Light Ends (PA Lites), uses a previously catego-rized waste as a raw material in its manufacture, thereby eliminating thematerial’s disposal via incineration. This Polyester Polyol is the basic rawmaterial for manufacture of various types of insulating wallboard used in thehome construction and commercial building industry. By substituting tradi-tional raw materials with PA Lites, Stepan Company is providing the con-struction industry and consumer a cost effective alternative to traditionalbuilding construction products. Using the phthalic anhydride distillation by-product as a raw material for the polyol process eliminates an entire wastestream. In 1994, 235,300 pounds of Phthalic Anhydride Light Ends was usedas a feedstock and 454,420 pounds were shipped out as a waste for fuelblending. In 1995, approximately 700,000 pounds of PA waste were used asa feedstock in the polyol process, thus eliminating an estimated 350 tons peryear of organic waste material. Benefits from this product substitution gobeyond eliminating a waste requiring disposal. With its substitution as a rawmaterial, it has reduced the requirement for phthalic anhydride, the tradi-tional raw material for the polyol product, and the air emissions associatedwith its manufacture. Since this previously categorized waste material is nowused on-site to produce Polyester Polyol, potential exposure to the generalpublic during off-site transportation to disposal facilities has been eliminated.This technology also provides significant cost savings. The savings associat-ed with the transportation and disposal via fuel blending for energy recoveryis expected to be $200,000 per year. The raw material savings due to thereplacement of pure PA with PA lites material on a pound per pound basisis $20,000 per year.

Tetrakishydroxymethyl Phosphonium Sulfate (THPS) Biocides

The United States industrial water treatment market for non-oxidizingbiocides is 40 million pounds per year and growing at six to eight percentannually. Tetrakishydroxymethyl phosphonium sulfate (THPS) biocides rep-resent a completely new class of antimicrobial chemistry that combines supe-rior antimicrobial activity with a relatively benign toxicology profile. THPSprovides a reduced risk to both human health and the environment whensubstituted for more toxic biocides. The human and environmental healthrisks of THPS have been compared with other biocides that currently com-prise an estimated 80 percent of the U.S. industrial water treatment market.THPS poses much less risk to the environment than many of the alternative

Stepan Company

Albright & WilsonAmericas Inc.

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products currently on the market. THPS biocides are aqueous solutions anddo not contain VOCs; they are also halogen-free and do not contribute todioxin or AOX formation. THPS does not bioaccumulate and can rapidlybreakdown through hydrolysis, oxidation, biodegradation, and photo-degra-dation before it enters the environment. The degradation products havebeen shown to be non-toxic. THPS is also the only biocide, compared tohigh volume alternatives, for which the typical dose rate is below the LC50 forfish. Because of its low overall toxicity when compared to alternative prod-ucts, THPS provides an opportunity to reduce the risk of health and safetyincidents.

Two-Stage Catalyst for NOx Reduction, CO Oxidation, andHydrocarbon Combustion in Oxygen Containing Exhaust Mixtures

A unique catalyst system has been developed for removing oxides ofnitrogen from automobile exhaust. These catalysts operate in a lean burnenvironment (excess oxygen in the engine) and represent a significantimprovement over existing technologies. Automobile manufactures prefer tooperate engines with excess oxygen to completely combust the fuel, improveefficiency, and reduce pollution. The principle impediment to designing suchan engine is the inability of existing exhaust system catalysts to reduce oxidesof nitrogen in the presence of oxygen. Some progress has been made inresolving this problem, specifically, copper impregnated zeolites are found toreduce oxides of nitrogen in the presence of oxygen. This material is not,however, without problems, including, low conversion of the oxides of nitro-gen. We have demonstrated a two stage catalysts system that significantlyimproves the conversion of oxides of nitrogen to environmentally acceptablegases. We have shown that a heterogeneous catalyst system consisting of twobeds in sequence, each containing a different catalytic material, is superiorfor the removal of NOx from exhaust streams containing oxygen, to the cur-rent generation of single stage catalysts. The character of each of the catalystbeds is fairly specific. The first bed consists of any high surface area refrac-tory oxide such as silica, alumina, titania, zirconia, ceria, zeolite, etc. The sec-ond bed consists of any metal loaded catalytic material known to reduce NOx

species in the presence of oxygen such as copper exchanged zeolite (e.g. Cu-ZSM-5). Many other materials, including zeolites exchanged with other met-als, high surface area silica or alumina impregnated with metals, also areknown to reduce NOx species in such environments, and thus also are can-didates for second bed materials.

Use of Carbon Dioxide as an Alternative Green Solvent for theSynthesis of Energetic Thermoplastic Elastomers

Thermoplastic elastomers based on triblock oxetane copolymers contain-ing azido functional groups offer an improved binding material for solid,high energy formulations. Current technology uses chemically cross-linkedenergetic prepolymer mixes that introduce the problems of thermally labilechemical linkages, high end-of-mix viscosities, and vulnerability to prema-

U.S. Department ofEnergy

Los Alamos NationalLaboratory

Professor Jonathan Phillips,Department of Chemical Engineering,Pennsylvania StateUniversity

U.S. Department of the Navy, Office of Naval Research

U.S. Department of the Navy, Naval Surface Warfare Center

41

ture detonation. These materials are also nonrecyclable and generate largeamounts of pollution during disposal. The use of energetic thermoplasticelastomers eliminates the need for chemical cross-linking agents, makes pro-cessing easier due to their low melt viscosities, and eliminates the need forsolvents during casting. Their superior processing qualities and the ease ofdemilitarization and recycling make these materials a much more environ-mentally sound choice for energetic binders. However, their synthesis stillinvolves the use of large quantities of toxic chemicals such as methylene chlo-ride as solvents. Carbon dioxide has been proven to be a viable, environmen-tally responsible replacement solvent for many synthetic and processingapplications. It is cheap, easily recyclable, and available from current sources.Research at the University of North Carolina has shown that carbon dioxide isa viable solvent for the polymerization of vinyl ether monomers. Furthermore,polyoxetanes can be polymerized in carbon dioxide with molecular weight,molecular weight distribution, and functionality maintained. The University ofNorth Carolina has demonstrated the synthesis of both nonenergetic and ener-getic homopolymers and random copolymers.

The Use of Chlorine Oxide, the Foundation of ElementalChlorine-Free Bleaching for Pulp and Paper, as a PollutionPrevention Process

The use of chlorine dioxide as part of a pollution prevention process tosubstantially or completely replace chlorine in the first stage of chemical pulpbleaching is a unique implementation of chlorine dioxide chemistry. It can beapplied to the entire bleached chemical pulp and paper industry, both in theUnited States and abroad. By employing raw material substitution andprocess modifications, this technology has allowed the pulp and paper indus-try to meet the source reduction objectives of the Pollution Prevention Act of1990. With this new application of sophisticated chlorine dioxide chemistry,the pulp and paper industry virtually eliminated dioxin from mill wastewaters and our nation’s water bodies. This technology has answered theindustry’s calls for a more benign chemical pulp bleaching agent. Virtualelimination of dioxin from mill waste waters and continuing nationwide eco-system recovery provide a strong measure of chlorine dioxide’s success andthe industry’s environmental progress. In fact, downstream of U.S. pulp millsbleaching with chlorine dioxide, fish dioxin body burdens have declinedrapidly and aquatic eco-systems continue to recover. For example, the MeadPaper Company’s Escanaba Mill in Michigan implemented pollution preven-tion strategies beginning with the use of low precursor defoamers in 1989, fol-lowed by increased substitution of chlorine by chlorine dioxide in 1990. Inless than four years, downstream dioxin body burdens declined more than 90percent. These indicators of progress toward broader eco-system integritydemonstrate the success of chlorine dioxide as “green chemistry.”

Professor Joseph DeSimone,

Department ofChemistry,

University of NorthCarolina

Aerojet Propulsion

Alliance forEnvironmental

Technology (AET)

42

Use, Regeneration, and Analysis of Aqueous Alkaline Cleaners

Lockheed Martin Tactical Aircraft Systems (LMTAS) was the first aero-space company to implement innovative aqueous cleaning technology forcleaning tubing and honeycomb core. Tubing is used in the aerospace indus-try for transferring pressurized oxygen within an aerospace vehicle.Honeycomb core is used in the aerospace industry for producing bondedstructural parts. Both applications require that the parts meet stringent clean-liness requirements. These requirements were previously met by using coldcleaning and/or vapor degreasing with chlorinated solvents such as 1,1,1-trichloroethane (TCA) and trichloroethylene (TCE), both of which are toxicand ozone depleting compounds. These solvents have been successfullyreplaced with LMTAS’ aqueous cleaning technology. Since May of 1994, 100percent of both tubing and honeycomb core manufactured at LMTAS havebeen cleaned using the aqueous cleaning technology. Coulometric titrationdata indicates that the LMTAS aqueous cleaning technology is as effective ormore effective than TCE vapor degreasing for cleaning aluminum tubing andhoneycomb core. In addition, implementation of the aqueous cleaning tech-nology at LMTAS has eliminated approximately 360 tons of air emissions peryear and has resulted in a cost savings of $490,000 per year. LMTAS also hasexplored the use of environmentally safe methods for quantifying surface con-taminants on parts cleaned by various cleaning technologies. Traditionally,extraction with CFC-113 followed by gravimetric or FTIR analysis has beenused for quantifying contaminants. LMTAS has demonstrated the usefulnessof carbon dioxide coulometry for determining the amount of residue remain-ing on a surface after cleaning and has used this technique for comparing thecleaning effectiveness of various cleaning technologies. Finally, LMTAS hasdemonstrated that ultrafiltration is a viable technology for the regeneration ofaqueous cleaners for reuse. Regeneration of aqueous cleaners can greatlyreduce replacement and disposal costs.

Waste Minimization in the Manufacture of an Antibiotic Producedby Chemical Synthesis

PRIMAXIN is an injectable, broad-spectrum antibiotic commercialized in1985. Development and implementation of an effective manufacturingprocess for PRIMAXIN was an immense challenge due in part to the com-plexity of the imipenem molecule and instability. The manufacturing processinitially proposed for PRIMAXIN involved 18 steps and would have createdone ton of waste for every pound of product. While still in the developmentlab, however, Merck’s chemists and engineers found a way to eliminate500,000 gallons of annual toxic waste. After production began, Merck con-tinued to improve the process by eliminating a mixture that prevented sol-vents from being reused, developing an innovative extractive hydrolysistechnology that improved yield, and reducing use of another solvent. Forexample, one of the process steps involved the use of methyl isobutyl ketone(MIBK) and acetonitrile. Process development work indicated that MIBKcould be eliminated. This allowed acetonitrile to be recycled, which previ-ously was sent off-site for disposal. In a separation step, the number of cyclesbetween regeneration of a chromatographic column using acetone/sulfuricacid was increased tenfold. These solvent recovery opportunities resulted in

Lockheed MartinTactical Aircraft Systems

Merck & Co., Inc.

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an annual savings of $50,000. Even after PRIMAXIN was in full scale man-ufacturing, several waste minimization process modifications were imple-mented that resulted in dramatic waste load reductions. The most significantis the 82 percent reduction in the use of methylene chloride by eliminatingmaterials that made methylene chloride recovery impractical, modifyingprocesses to allow the use of recovered material, and improving recoverytechniques. This dramatic waste reduction resulted in an annual savings ofover $1 million, and the process is still undergoing modification in order tofurther reduce waste generation. Development, implementation, and ongoingimprovement of the process to manufacture PRIMAXIN (imipenem) is aprime example of Merck’s contribution to the promotion of environmentallybenign technology.

Waste Reduction in the Production of an Energetic Material byDevelopment of an Alternative Synthesis

1,3,3-Trinitroazetidine (TNAZ) is a promising new melt-castable explosivethat has significant potential for providing environmental benefits and capa-bility improvements in a wide variety of defense and industrial applications.Initial life-cycle inventories on various munitions revealed that up to 50 per-cent of the life-cycle pollution burden was associated with the demilitarizationof the munitions, and in particular, the use of thermoset polymeric bindersthat require removal with water jet cutting. TNAZ is the only energetic mate-rial other than trinitrotoluene (TNT) that can be melt-cast in existing TNTloading plants. Demilitarization of TNAZ simply requires heating the deviceabove the melting point and pouring the liquid out, rather than the compli-cated and destructive methods used for RDX- and HMX-based plastic-bond-ed explosives. The stability of TNAZ in the melt allows it to be easilyrecycled. TNAZ has performance slightly greater than that of HMX, the mostpowerful military explosive in current use. Thus, TNAZ may offer 30-40 per-cent improvements in performance as a replacement for TNT-based formula-tions such as Composition-B. The alternative synthesis of TNAZ developed atthe Los Alamos National Laboratory allows TNAZ to be produced in a waste-free process that also eliminates the use of halogenated solvents. This alterna-tive synthesis produces 5.3 pounds of waste per pound of product comparedto the original synthesis of TNAZ which produces 1200 pounds of waste perpound of product. The alternate technology has been transferred to industry,where it has been scaled up to production-plant quantities. Further improve-ments in waste reduction have been demonstrated in the laboratory that mayeventually lead to a process giving little more waste than one pound of saltper pound of TNAZ.

Water-Dispersible Sulfopolyester for Reduced VOC Consumer Products

The reduction of airborne emissions is a major focal point for legislationto safeguard public health. Volatile organic compounds (VOCs) are one ofthe major sources of air pollution that arise from both consumer and indus-trial products. Legislation proposed at the state level, particularly in

U.S. Departmentof the Navy,

Office of Naval Research

U.S. Departmentof the Navy,

Naval SurfaceWarfare Center

U.S. ArmyArmamentResearch,

Developmentand Engineering

Center

Los Alamos National Laboratory

Aerojet

Eastman ChemicalCompany

44

California, is targeting consumer and personal care products for VOC con-tent reductions. One of the largest product areas is in hairsprays, which avery large, diverse segment of the population uses daily. Consumers, how-ever, demand that “green” products have the same if not better performancecharacteristics. Eastman Chemical Company has developed a new product,known as EASTMAN AQ 48 Ultra, for this general need that not onlyreduces VOCs, but actually may improve performance. EASTMAN AQ 48Ultra is a water-dispersible sulfopolyester that allows hairsprays to be for-mulated with 55 percent ethanol, which is significantly less than the currentindustry standard of 80 percent VOC. Switching all of the hairspray marketfrom the current standard of 80 percent VOC to 45 percent VOC wouldresult in a total reduction of VOC emissions around 55 million pounds peryear. In general, sulfopolyester dispersions may be used as low VOC film-formers for a variety of cosmetic products in addition to hairsprays; there-fore, an even larger potential for VOC emission reduction exists. Finally, theprocess chemistry is completed in the melt phase. There are no organic sol-vents used in the synthesis of sulfopolyesters at Eastman ChemicalCompany. The synthesis also does not release any toxic by-products.

The Green Chemistry Challenge is a voluntary program that operatesthrough a broad consortium that includes members of the chemical indus-try, trade associations, scientific organizations, and representatives fromacademia. The program is open to all individuals, groups, and organiza-tions involved in chemical design, manufacture and use.

Additional Information about the Green Chemistry Challenge is avail-able from EPA’s homepage on the internet (http://www.epa.gov; select“Offices,” then “Prevention, Pesticides, and Toxic Substances,” then“Toxics”) and from EPA’s Toxic Substance Control Act AssistanceInformation Service (202-554-1404; TDD: 202-554-0551), or call EPA’sIndustrial Chemistry Branch at 202-260-2659.

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IndexAward winners are indicated with *.

Advanced Micro Devices (AMD), Austin Environmental DepartmentThe Emission Quantification Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27

Albright & Wilson Americas Inc.Tetrakishydroxymethyl Phosphonium Sulfate (THPS) Biocides . . . . . . . . . . . . .39

Alliance for Environmental Technology (AET)The Use of Chlorine Oxide, the Foundation of Elemental Chlorine-Free Bleaching for Pulp and Paper, as a Pollution Prevention Process . . . . . . . . . . . .41

Altus Biologics Inc.Cross-Linked Enzyme Crystal Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . .12

Anderson, Marc A., Water Chemistry Program, University ofWisconsin-MadisonGreen Technology for the 21st Century: Ceramic Membranes . . . . . . . . . . . . . . . .9

Asarco IncorporatedAsarco — West Fork Biotreatment Project . . . . . . . . . . . . . . . . . . . . . . . . . . . .20

Bayer CorporationAldimine-Isocyanate Chemistry: a Foundation for Environmentally-Friendly High Solids Coatings . . . . . . . . . . . . . . . . . . . . . . .15

Benchmark Products, Inc.Development of a Nickel Brightener Solution . . . . . . . . . . . . . . . . . . . . . . . . .13

BF Goodrich and Tremco, a BF Goodrich CompanyDevelopment of a New Sealant/Adhesive Chemistry for Automotive Windshields. ANew Two Part Chemical System Using Acetoacetylated Polyol Prepolymers andAminated Acetoacetylated Polyol Prepolymers. . . . . . . . . . . . . . . . . . . . . . . . . .23

BHC Company (Hoechst Celanese Corporation)The BHC Company Ibuprofen Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21

Bureau of Engraving and Printing, Office of Research and Technical SupportAn Alternative Solvent, Isomet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .17

California-Pacific Lab & ConsultingThe ECO Funnel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26

Circuit Research CorporationA Non-Toxic, Non-Flammable, Aqueous-Based Cleaner/Degreaser and Associated Parts Washing System Commonly Employed in Automotive Repair Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15

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CTS Corporation Resistor NetworksNo-Clean Soldering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .36

DeSimone, Joseph, Department of Chemistry, University of North Carolina at Chapel Hill, Air Products and Chemicals, Inc. Soapy CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11

*Donlar Corporation*Production and Use of Thermal Polyaspartic Acid . . . . . . . . . . . . . . . . . . . . . .5

*The Dow Chemical Company*The Development and Commercial Implementation of 100 Percent Carbon Dioxide as an Environmentally Friendly Blowing Agent for the Polystyrene Foam Sheet Packaging Market . . . . . . . . . . . . . . . . . . . . . . . . .3

The Dow Chemical Company’s Novel INVERTTM Solvents . . . . . . . . . . . . . . . .25

Dumesic, James A., Chemical Engineering Department, Universityof Wisconsin and John C. Crittenden, National Center for CleanIndustrial and Treatment Technologies, Michigan TechnologicalUniversityRational Design of Catalytic Reactions for Pollution Prevention . . . . . . . . . . . .10

DuPont CompanyThe DuCare “Zero Effluent” Recycle Chemistry System . . . . . . . . . . . . . . . . . .26

The INFINITY Dyeing Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28

NAFION Membrane Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32

Eastman Chemical CompanyWater-Dispersible Sulfopolyester for Reduced VOC Consumer Products . . . . . . .43

Eastman Kodak CompanyPolycarbonate/Polydimethylsiloxane Copolymers for Thermal Print Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37

GE Plastics (General Electric Corporation)New Catalyst for Producing ULTEM ® Thermoplastic Resin . . . . . . . . . . . . . . .35

Hatton, T. Alan, Department of Chemical Engineering,Massachusetts Institute of Technology, and Stephen L. Buchwald,Chemistry Department, Massachusetts Institute of TechnologyDerivatized and Polymeric Solvents for Minimizing Pollution during the Synthesis of Pharmaceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8

Hendrickson, James B., Department of Chemistry, BrandeisUniversityThe SYNGEN Program for Generation of Alternative Syntheses . . . . . . . . . . . .11

Henkel Corporation, Emery GroupAlkyl Polyglycoside Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16

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*Holtzapple, Mark, Department of Chemical Engineering, Texas A&M UniversityConversion of Waste Biomass to Animal Feed, Chemicals, and Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7

Hudlicky, Tomas, Department of Chemistry, University of FloridaEnzyme-Assisted Conversion of Aromatic Substances to Value-Added End Products. Exploration of Potential Routes to Biodegradable Materials and New Pharmaceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8

Hughes Environmental Systems, Inc. DryWashTM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25

IBM-AustinElimination of Ozone-Depleting Chemicals in the Printed Wire Board andElectronic Assembly and Test Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27

Innovative Techniques for Chemical and Waste Reductions in the Printed WireBoard Circuitize Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .29

Lockheed Martin Tactical Aircraft Systems Development and Implementation of Low Vapor Pressure Cleaning Solvent Blends and Waste Cloth Management Systems to Capture Cleaning Solvent Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22

Use, Regeneration, and Analysis of Aqueous Alkaline Cleaners . . . . . . . . . . . . .42

Los Alamos National Laboratory Application of Freeze Drying Technology to the Separation of Complex Nuclear Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18

Application of Green Chemistry Principles to Eliminate Air Pollution from the Mexican Brickmaking Microindustry . . . . . . . . . . . . . . . . . . . . . . . . .19

Magnetic Separation for Treatment of Radioactive Liquid Waste . . . . . . . . . . . .31

A Microwave Oven Dissolution Procedure for a Ten Gram Sample of Soil Requiring Radiochemical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31

Solvent Replacement and Improved Selectivity in Asymmetric Catalysis UsingSupercritical Carbon Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .38

Mallinckrodt Chemical, Inc. The Removal of Oxides of Nitrogen by In Situ Addition of Hydrogen Peroxide to a Metal Dissolving Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37

Merck & Co., Inc.Waste Minimization in the Manufacture of an Antibiotic Produced by Chemical Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .42

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Molten Metal Technology, Inc.Catalytic Extraction Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12

*Monsanto Company*The Catalytic Dehydrogenation of Diethanolamine . . . . . . . . . . . . . . . . . . . . .2

Roundup ReadyTM Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .38

Nalco Chemical CompanyNalco NALMET ® . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .33

Nalco PORTA-FEED ® Advanced Chemical Handling Systems . . . . . . . . . . . .33

Nalco TRASAR ® Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .34

Nalco ULTIMERTM Polymer Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . .35

Nalco Fuel TechNalco Fuel Tech NOxOUT ® Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32

Paquette, Leo A., Department of Chemistry, Ohio State UniversityEnvironmental Advantages Offered by Indium-Promoted Carbon-CarbonBond-Forming Reactions in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8

Pharmacia and Upjohn, Inc.An Alternative Synthesis of Bisnoraldehyde, an Intermediate to Progesterone and Corticosteroids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18

Praxair, Inc.Liquid Oxidation Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .30

Recombinant BioCatalysis, Inc. (RBI)Development of a Biodiversity Search and Enzyme Optimization Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13

Rochester Midland CorporationDevelopment of a New “Core” Line of Cleaners . . . . . . . . . . . . . . . . . . . . . . .22

*Rohm and Haas Company* Designing an Environmentally Safe Marine Antifoulant . . . . . . . . . . . . . . . . .4

Invention and Commercialization of CONFIRMTM Selective Caterpillar Control Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .30

Sandoz Pharmaceutical CorporationDevelopment of a New Process for the Manufacture ofPharmaceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .23

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Shaw, Henry, Chemistry and Environmental Science Department,New Jersey Institute of Technology and Dan Watts, Center forEnvironmental Engineering and Science, New Jersey Institute ofTechnologyThe Replacement of Hazardous Organic Solvents with Water in the Manufacture of Chemicals and Pharmaceuticals . . . . . . . . . . . . . . . . . . . . . . .10

Stanson CorporationNational Conversion to Low Sudsing Hand Dish Detergents for Industrial,Institutional, and Especially Consumer Application . . . . . . . . . . . . . . . . . . . . .14

Stepan CompanyStepan Company PA Lites Polyester Polyol . . . . . . . . . . . . . . . . . . . . . . . . . .39

Taylor, Larry T., Department of Chemistry, Virginia Tech; Virginia Tech Intellectual PropertiesA Nontoxic Liquid Metal Composition for Use as a Mercury Substitute . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9

Technic, Inc.; U.S. Department of Energy; and Lawrence Livermore National LaboratoryNon-Cyanide Silver Electroplating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .36

Texaco Inc.CleanSystem3 Gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21

U.S. Department of Defense, Office of Munitions; U.S. Department of Energy, Weapons Supported Research; and Lawrence Livermore National LaboratoryEnvironmentally-Driven Preparation of Insensitive Energetic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28

U.S. Department of Energy, Office of Industrial Technologies ProgramsThe Alternative Feedstocks and Biological and Chemical Technologies Research Programs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .17

U.S. Department of Energy, Office of Pollution Prevention, DOE Office of Energy Research, DOE Chicago Operations Office, DOE Argonne Group and Argonne National LaboratoryApplication of Microchemistry Technology to the Analysis of Environmental Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .20

U.S. Department of Energy; Pacific Northwest National LaboratoryDOE Methods for Evaluating Environmental and Waste Management Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25

U.S. Department of Energy; Los Alamos National Laboratory; andProfessor Jonathan Phillips, Department of Chemical Engineering,Pennsylvania State UniversityTwo-Stage Catalyst for NOx Reduction, CO Oxidation, and HydrocarbonCombustion in Oxygen Containing Exhaust Mixtures . . . . . . . . . . . . . . . . . . .40

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U.S. Department of the Navy, Office of Naval Research; U.S.Department of the Navy, Naval Surface Warfare Center; Professor Joseph DeSimone, Department of Chemistry, University of North Carolina; and Aerojet PropulsionUse of Carbon Dioxide as an Alternative Green Solvent for the Synthesis of Energetic Thermoplastic Elastomers . . . . . . . . . . . . . . . . . . . . . . .40

U.S. Department of the Navy, Office of Naval Research; U.S. Department of the Navy, Naval Surface Warfare Center; U.S. ArmyArmament Research, Development and Engineering Center; Los Alamos National Laboratory; and AerojetWaste Reduction in the Production of an Energetic Material by Development of an Alternative Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . .43

Zeller InternationalEnviroblock Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .14